Process for the preparation of polyolefin-based graft copolymers comprising a first long chain branched polyolefin block and one or multiple polymer side chains

ABSTRACT

The present invention relates to a process for the preparation of polyolefin-based graft copolymers comprising a first long chain branched polyolefin block and one or multiple polymer side chains. The functionalized long chain branched polyolefin is produced via the copolymerization of an olefin monomer and an olefin bearing a main group metal hydrocarbyl functionality. The invention moreover relates to polyolefin obtained by said process ends. Subsequently the graft copolymers according to the invention can be produced for example by ring-opening polymerization of cyclic monomers or by transesterification of a preformed transesterifiable polymer, especially polyesters or polycarbonates. The invention moreover relates to polyolefin-based graft copolymers obtained by said process.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage application of PCT/EP2016/078295,filed Nov. 21, 2016, which claims the benefit of European ApplicationNo. 15198656.9, filed Dec. 9, 2015, both of which are incorporated byreference in their entirety herein.

The present invention relates to a process for the preparation ofpolyolefin-based graft copolymers comprising a first long chain branchedpolyolefin block and one or multiple polymer side chains. Thefunctionalized long chain branched polyolefin is produced via thecopolymerization of an olefin monomer and an olefin bearing a main groupmetal hydrocarbyl functionality according to Formula 1a. The inventionmoreover relates to polyolefin obtained by said process ends.Subsequently the graft copolymers according to the invention can beproduced for example by ring-opening polymerization of cyclic monomersor by transesterification of a preformed transesterifiable polymer,especially polyesters or polycarbonates. The invention moreover relatesto polyolefin-based graft copolymers obtained by said process.

BACKGROUND

The present invention relates to the preparation of polyolefin-basedgraft copolymers comprising a first long chain branched polyolefin blockand one or multiple polymer side chains, the intermediate products andthe processes to obtain these products.

Commercially available polyethylene and polypropylene prepared usingstandard procedures with Ziegler-Natta or single-site catalysts have apredominantly linear molecular structure. Although linear polyolefinshave many desirable physical properties, they show a variety of meltprocessing shortcomings, especially the single-site prepared ones havingnarrow molecular weight distributions, which typically have a low meltstrength. Low melt strength is a problem because it causes localthinning in melt thermoforming, relative weakness in large-part blowmolding and flow instabilities in co-extrusion of laminates.

One way of overcoming the shortcomings of linear polyolefins is by meansof branching, viz. the provision of polymer side chains extending fromthe polyolefin backbone.

Despite their ubiquitous presence in our society, polyolefins such aspolyethylene and polypropylene are not appropriate for severalapplications as a consequence of their inherently nonpolar character.This nonpolar character is the reason for the poor adhesion,printability and compatibility that can restrict their efficacy. Hence,it is further desirable to prepare polyolefins bearing for example polargroups so to ensure a good adhesion and printability.

In the prior art copolymers have thus been prepared and considered toovercome the shortcomings of polyolefins mentioned above. However, thepreparation of these copolymers is often complicated and cumbersome.Moreover, most preparation methods lack flexibility.

The present invention is directed towards an easy, catalyst-compatible,relatively inexpensive and safe process that can be used for large scalepreparation of polyolefin-based graft copolymers comprising a first longchain branched polyolefin block and one or multiple polymer side chains.

SUMMARY OF THE INVENTION

In a first aspect, the present invention relates to a process for thepreparation of polyolefin-based graft copolymers comprising a first longchain branched polyolefin block and one or multiple polymer side chains,said process comprising the step of:

-   -   A) a polymerization step comprising copolymerizing at least one        first type of olefin monomer, preferably selected for example        from ethylene or propylene, and at least one second type of        olefin monomer comprising a main group metal hydrocarbyl        functionality according to Formula 1a: R¹⁰⁰        _((n-2))R¹⁰¹M^(n+)R¹⁰² using a catalyst system to obtain a        polyolefin; wherein said catalyst system comprises a co-catalyst        and/or a scavenger and a catalyst or catalyst precursor        comprising a metal from Group 3-10 of the IUPAC Periodic Table        of elements that can undergo chain transfer polymerization with        the main group metal hydrocarbyl functionality of the second        type of olefin monomer or that via a chain shuttling agent can        undergo chain transfer polymerization with the main group metal        hydrocarbyl functionality of the second type of olefin monomer        and

wherein further M is a main group metal; n is the oxidation state of M;R¹⁰⁰, R¹⁰¹ and R¹⁰² of Formula 1a are each independently selected fromthe group consisting of a hydride, a C1-C18 hydrocarbyl group, a halide,an alkoxide, an amide, a thiolate or a hydrocarbyl group Q on theproviso that at least one of R¹⁰⁰, R¹⁰¹ and R¹⁰² is a hydrocarbyl groupQ, wherein hydrocarbyl group Q is according to Formula 1b:

-   -   wherein Z is bonded to M and Z is a C1-C18 hydrocarbyl group;        R¹⁰⁵ optionally forms a cyclic group with Z; wherein R¹⁰³ and        R¹⁰⁴ and R¹⁰⁵ are each independently selected from hydrogen or a        hydrocarbyl group; and at least one step of:    -   B) an oxidizing step comprising contacting said polyolefin        obtained in step A) with at least one oxidizing agent to obtain        a polyolefin having one or more pending oxidized        functionalities; and/or    -   C) contacting said polyolefin obtained in step B) with at least        one quenching agent to obtain a polyolefin having one or more        pending polar functionalities,    -   D) using the polyolefin having one or more pending polar        functionalities obtained in step C) to obtain a graft copolymer        by transesterification of a preformed transesterifiable polymer        and/or by ring-opening polymerization of cyclic monomers,        especially cyclic esters (lactones) and/or cyclic carbonates.

A polyolefin having one or more pending polar functionalities may be apolyolefin having a backbone preferably for example made of ethylene orpropylene as well as of an olefin monomer comprising a main group metalhydrocarbyl functionality, as produced in step A), which has beingsubjected to an oxidative treatment in step B). The metal hydrocarbylfunctionality of the second monomer can function as a chain transferagent, giving rise to coordinative chain transfer polymerization. As aresults of this, long chain branched polymers might be obtained havingmain group metal hydrocarbyl functionalities at the end of thechains/branches. Since the branches are actually growing chains as aresult of the chain transfer process, they can also incorporate more ofthe second type of monomer, which will result in branches-on-branchesstructures. The second type of olefin monomer comprising a main groupmetal hydrocarbyl functionality can thereby comprise a spacer, like forexample a substituted and/or unsubstituted alkyl chain and/or bridged orunbridged, substituted and/or unsubstituted, cyclic hydrocarbon, linkingthe olefin and the main group metal hydrocarbyl functionality. Thesecond type of olefin monomer comprising a main group metal hydrocarbylfunctionality can thereby comprise bridged or unbridged, substitutedand/or unsubstituted, cyclic hydrocarbon as a spacer for example when areactive cyclic olefin, especially for example a norbornene derivativecomprising a main group metal hydrocarbyl functionality is used as thesecond type of olefin monomer.

A long chain branch can also preferably for example comprisebetween >100 to 100,000,000 carbon atoms, preferably between 500 to10,000,000 carbon atoms, even more preferred between 1000 to 1,000,000carbon atoms, more preferred between 10,000 to 500,000 carbon atoms,more preferred between 20,000 to 200,000 carbon atoms, preferably in thebackbone, of the long chain branch. A long chain branch can alsopreferably for example be long enough to lead to entanglement phenomena,preferably involving the branch.

Pending polar functionalities may mean a functionality that preferablycomprises at least one heteroatom that is different from carbon andhydrogen. Such a heteroatom may thereby be preferably moreelectronegative than carbon and/or hydrogen. A polar functionality canespecially comprise for example a hydroxyl, carboxylic acid, amine orhalogen functionality.

A heteroatom may be preferably for example selected from Group 14, 15,16 or 17 of the IUPAC Periodic Table of the Elements and can as used inthe present description for example especially mean a hetero atomselected from Si, Ge, Sn [Group 14], N, P, As, Sb, Bi [Group 15], O, S,Se, Te [Group 16] or halogens [Group 17].

Hydrocarbyl as used in the present description may means: a substituentcontaining hydrogen and/or carbon atoms; it may for example be a hydrideor a linear, branched or cyclic saturated or unsaturated aliphaticsubstituent, such as for example alkyl, alkenyl, alkadienyl and alkynyl;alicyclic substituent, such as cycloalkyl, cycloalkadienyl cycloalkenyl;aromatic substituent or aryl, such as for example monocyclic orpolycyclic aromatic substituent, as well as combinations thereof, suchas alkyl-substituted aryls and aryl-substituted alkyls. It may besubstituted with one or more non-hydrocarbyl, heteroatom-containingsubstituents or heteroatoms. Hence, when in the present descriptionhydrocarbyl is used it can also mean a substituted hydrocarbyl, unlessstated otherwise. Included in the term “hydrocarbyl” are alsoperfluorinated hydrocarbyls wherein all hydrogen atoms are replaced byfluorine atoms. A hydrocarbyl may moreover for example be present as agroup on a compound (hydrocarbyl group) or it may be present as a ligandon a metal (hydrocarbyl ligand).

Alkyl as used in the present description means: a group consisting ofcarbon and hydrogen atoms having only single carbon-carbon bonds. Analkyl group may be straight or branched, un-substituted or substituted.It may contain aryl substituents. It may or may not contain one or moreheteroatoms.

Aryl as used in the present description means: a substituent derivedfrom an aromatic ring. An aryl group may or may not contain one or moreheteroatoms. An aryl group also encloses substituted aryl groups whereinone or more hydrogen atoms on the aromatic ring have been replaced byhydrocarbyl groups.

Hydride as used in the present description may mean: a hydrogen anionbonded to a metal.

In an embodiment, at least one of R¹⁰⁰, R¹⁰¹ and R¹⁰² of Formula 1a canbe a hydrocarbyl group Q and the remaining groups of R¹⁰⁰, R¹⁰¹ and R¹⁰²are each a C1-C18 hydrocarbyl group, preferably a C1-C10 hydrocarbylgroup or wherein two groups of R¹⁰⁰, R¹⁰¹ and R¹⁰² are each ahydrocarbyl group Q and the remaining group of R¹⁰⁰, R¹⁰¹ and R¹⁰² is aC1-C18 hydrocarbyl group, preferably C1-C10 hydrocarbyl group, furtherpreferred a C1-C4 hydrocarbyl group, or wherein all of R¹⁰⁰, R¹⁰¹ andR¹⁰² are a hydrocarbyl group Q. Expressions like for example “C1-C4” or“C1-C16” and similar formulations may refer to a range regarding anumber of carbon atoms, here for example respectively from 1 to 4 orfrom 1 to 16 carbon atoms.

In an embodiment, a second type of olefin monomer comprising a maingroup metal hydrocarbyl functionality can be selected from the groupconsisting of bis(isobutyl)(5-ethylen-yl-2-norbornene) aluminum,di(isobutyl)(7-octen-1-yl) aluminum, di(isobutyl)(5-hexen-1-yl)aluminum, di(isobutyl)(3-buten-1-yl) aluminum,tris(5-ethylen-yl-2-norbornene) aluminum, tris(7-octen-1-yl) aluminum,tris(5-hexen-1-yl) aluminum, or tris(3-buten-1-yl) aluminum,ethyl(5-ethylen-yl-2-norbornene) zinc, ethyl(7-octen-1-yl) zinc,ethyl(5-hexen-1-yl) zinc, ethyl(3-buten-1-yl) zinc,bis(5-ethylen-yl-2-norbornene) zinc, bis(7-octen-1-yl) zinc,bis(5-hexen-1-yl) zinc, or bis(3-buten-1-yl) zinc. A cyclic unsaturatedhydrocarbyl group can thereby lead for example to a high reactivity.

In an embodiment, the catalyst or catalyst precursor used in step A) maycomprise a metal from Groups 3-10 of the IUPAC Periodic Table ofelements, more preferably from Groups 3-8 from Groups 3-6 and/or whereinthe metal catalyst or metal catalyst precursor used in step A) comprisesa metal selected from the group consisting for example of Ti, Zr, Hf, V,Cr, Fe, Co, Ni, Pd, preferably Ti, Zr or Hf.

In an embodiment, said catalyst can be a Ziegler-Natta catalyst, such asfor example titanium-magnesium and aluminum based Ziegler-Nattacatalysts, especially obtained for example by reacting a titanium alkoxywith a magnesium alkoxy and subsequently reaction the reaction productwith an aluminum alkyl halide, or a catalyst based on a Group 4 metal,which can especially be for example a metallocene, half-metallocene or apost-metallocene and/or a single-site catalyst.

In an embodiment, a catalyst precursor can be for example a C_(s)-, C₁-or C₂-symmetric zirconium or hafnium metallocene, preferably an indenylsubstituted zirconium or hafnium dihalide, more preferably a bridgedbis-indenyl zirconium or hafnium dihalide, even more preferablyrac-dimethyl silyl bis-indenyl zirconium or hafnium dichloride(rac-Me₂Si(Ind)₂ZrCl₂ and rac-Me₂Si(Ind)₂HfCl₂, respectively), orrac-dimethylsilyl bis-(2-methyl-4-phenyl-indenyl) zirconium or hafniumdichloride (rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ andrac-Me₂Si(2-Me-4-Ph-Ind)₂HfCl₂, respectively).

In an embodiment, said catalyst precursor can be for example a so-calledhalf-metallocene, or constrained geometry catalyst, even morepreferably, C₅Me₅[(C₆H₁₁)₃P═N]TiCl₂, [Me₂Si(C₅Me₄)N(tBu)]TiCl₂,[C₅Me₄(CH₂CH₂NMe₂]TiCl₂. In an embodiment, said catalyst can be forexample a so-called post-metallocene, preferably[Et₂NC(N(2,6-iPr₂—C₆H₃)]TiCl₃ or[N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl.

For example oxygen, ozone or oxygen-containing gas mixtures such as airor synthetic air or mixtures of oxygen with other gases can be used asoxidizing agents in step B).

Moreover, at least one safe oxidation agent can for example be used instep B).

In an embodiment, at least safe oxidizing agent according to theinvention used in step B) can for example be preferably selected fromthe group consisting of CO, CO₂, CS₂, COS, N₂O and SO₃, preferably, N₂O,CO₂ and SO₃ or mixtures of at least two or more thereof, even morepreferably CO₂. A safe oxidizing agent in the sense of the presentinvention, can thereby be for example be an compound where at least oneoxygen is bound at least one other atom then oxygen and/or a compoundcomprising at least one nitrogen-carbon CN double or triple bond. Usingsafe oxidants according to the present invention thereby allows reducingthe process risk (especially for example the risk of fire andexplosions) associated with the use of the oxidizing agent, so as to beable to easily scale up the reactions and/or use high pressures. Usingmore than one oxidizing agents can thereby for example lead to polymershaving at least two or more different polar functionalities.

The inventors could thereby surprisingly show that the use of safeoxidizing agents did lead to an oxidation and/or functionalization yieldequal or higher than with gaseous oxygen or oxygen containing gasmixtures could be obtained. Oxidation and/or functionalization yield canthereby preferably for example be >50%, preferred >60%, furtherpreferred >70% or even further preferred >80%.

In a second aspect, the invention relates to a polyolefin having acontent of polar functionalities of for example at most 0.1 mol-%, atmost 1 mol-%, at most 3 mol-%, at most 5 mol-%, 10 mol-% and/or at least0.001 mol-%, at least 10 mol-%, at least 15 mol-%, 25 mol-%, preferablyat least 30 mol-%.

During step C) a quenching agent can be used to obtain preferably apolar function, like for example a hydroxyl function, at the branches.

In an embodiment, the reagent is a protic reagent. In a preferredembodiment the protic agent is water or an alcohol or a mixture thereof,preferably water.

It is possible that in a specific embodiment instead of a hydrolysisanother type of quenching step is carried out. Said step is thenpreferably carried out using a non-protic metal-substituting quenchingagent.

The present invention will be described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION

The present invention concerns the copolymerization of an olefinmonomer, preferably ethylene or propylene, and at least one second typeolefin monomer, preferably also α-olefin, containing a main group metalhydrocarbyl functionality, to obtain long chain branches via chaintransfer polymerization.

Thus, it can be said that the intermediate that is desired in thepresent invention is a polyolefin having one or multiple preferably longchain branches. The copolymer obtained in step A) can thereby beoxidized and/or optionally subsequently quenched to produce the desiredend product.

Subsequently the graft copolymers according to the invention can beproduced for example by ring-opening polymerization (ROP) of cyclicmonomers and/or by transesterification of a preformed transesterifiablepolymer, especially polyesters or polycarbonates. A transesterifiablepolymer in the sense of the invention may thereby be for example apolyester, a polycarbonate, a polyamide, a polyurethane, a polyurea, arandom or block poly(carbonate-ester), poly(carbonate-ether),poly(ester-ether), poly(carbonate-ether-ester), poly(ester-amide),poly(ester-ether-amide), poly(carbonate-amide),poly(carbonate-ether-amide), poly(ester-urethane),poly(ester-ether-urethane), poly(carbonate-urethane),poly(carbonate-ether-urethane), poly(ester-urea),poly(ester-ether-urea), poly(carbonate-urea),poly(carbonate-ether-urea), poly(ether-amide), poly(amide-urethane),poly(amide-urea), poly(urethane-urea) or one or more combination(s)thereof. The invention moreover relates to polyolefin-based graftcopolymers obtained by said process.

This can for example be used for the preparation of polyolefins havingpending polar functionalities via an additional oxidation step.

The present invention uses an olefin-comprising main group metalhydrocarbyl as comonomer. In other words, the olefin-comprising maingroup metal hydrocarbyl can be, for example, an alkene-comprisingaluminum hydrocarbyl or an alkene-comprising zinc hydrocarbyl.

Step A):

The first step in the process according to the present invention is thepreparation of a polyolefin having one or multiple main group metalfunctionalized branches by polymerizing at least one first type ofolefin monomer, preferably a α-olefin, and at least one second type ofolefin monomer, preferably an α-olefin, comprising a main group metalhydrocarbyl functionality, which functionalities as a chain transferagent, with a metal catalyst that might undergo chain transferpolymerization with the main group metal hydrocarbyl functionality ofthe second type of olefin monomer either with or without chain shuttlingagent, optionally a co-catalyst, optionally a scavenger and optionallyone or more additional chain transfer agents and/or chain shuttlingagents. In an embodiment, said main group metal hydrocarbylfunctionality or a corresponding functionality can for example be analkenyl-comprising aluminum hydrocarbyl or a correspondingfunctionality.

The second type of olefin monomer can comprise a main group metalhydrocarbyl functionality, which can for example be a reactiveelectrophilic metal group, which functionalities as a chain transferagent. The metal hydrocarbyl functionality of the second monomer canfunction as a chain transfer agent, giving rise to coordinative chaintransfer polymerization. As a results of this, long chain branchedpolymers might be obtained having main group metal hydrocarbylfunctionalities at the end of the chains/branches. Since the branchesare actually growing chains as a result of the chain transfer process,they can also incorporate more of the second type of monomer, which willresult in branches-on-branches structures. The resulting polyolefin canhave one or multiple branches comprising at least one reactiveelectrophilic metal functionality, preferably for example at the end ofthe branch(es). In other words, said product is a branched polyolefinthat is functionalized on at least one of its branches with a main groupmetal.

A “main group metal” as used in the present description can referto/mean: a metal that is of a main group, namely an element of groups 1,2, and 13-15 of the period table or zinc. In other words, metals of:

-   -   Group 1: lithium (Li), sodium (Na), and potassium (K)    -   Group 2: beryllium (Be), magnesium (Mg), and calcium (Ca)    -   Group 13: boron (B), aluminum (Al), gallium (Ga), and indium        (In)    -   Group 14: germanium (Ge), and tin (Sn)    -   Group 15: antimony (Sb), and bismuth (Bi) of the IUPAC Periodic        Table of elements    -   main group metals also include for the context of the present        invention zinc (Zn).

During the polymerization reaction according to step A) at least oneolefin comprising a main group metal hydrocarbyl functionality (beingfor example a main group metal atom bearing one or more hydrocarbyland/or hydride groups and at least one alkenyl group) is used. Theproduct obtained in step A) is then a polyolefin having one or multiplemain group metal-functionalized branches (being a branched polyolefinthat is functionalized on at least one of its branches with a main groupmetal). This is considered to be the main product of step A), which isan intermediate product in the process according to the presentinvention.

The catalyst system used in step A) comprises: i) a Group 3-10,preferably Group 3-8 and more preferably Group 3-6, metal catalyst ormetal catalyst precursor as well as optionally one or more of ii) aco-catalyst, iii) a scavenger and/or iv) optionally one or more chaintransfer agents and/or chain shuttling agents.

According to the present invention, the catalyst can be selected,preferably so that it may lead to an interaction, especially to chaintransfer, preferably without poisoning, with the main group metalhydrocarbyl functionality of the second type of olefin monomer. Acatalyst that does lead to an interaction and/or to chain transferpolymerization may thereby preferably for example be a catalyst thatdoes lead to interaction products detectable by NMR and/or to chaintransfer products detectable by NMR and/or viscosity measurements. Anexample of a selection made in that way, may be the selection of acatalyst comprising zirconium (Zr) or titanium (Ti) as the metal, forexample rac-Me₂Si(Ind)₂ZrCl₂, and of a main group metal hydrocarbylfunctionality comprising aluminum (Al) as the metal for the second typeof olefin monomer, since it is known that such a catalyst in thepresence of a chain shuttling agent, preferably diethyl zinc, will leadto chain transfer polymerization with an aluminum hydrocarbylfunctionality. In the sense of the present invention, poisoning maythereby for example a poisoning that may reduce catalyst activity by atleast 50%, preferably by at least 25%, further preferred by at least20%, even further preferred by at least 15%, even further preferred byat least 10%, even further preferred by at least 5%, even furtherpreferred by at least 3%, even further preferred by at least 1%, evenfurther preferred by at least 0.5%. Moreover, chain transferpolymerization in the sense of the present invention may thereby forexample be a chain transfer polymerization that accounts for at least50%, preferably by at least 25%, further preferred by at least 20%, evenfurther preferred by at least 15%, even further preferred by at least10%, even further preferred by at least 5%, even further preferred by atleast 3%, even further preferred by at least 1%, even further preferredby at least 0.5% of the polymer material produced by polymerizationaccording to the process of the present invention.

This may preferably allow the formation of polymers with long chainbranches by polymerizing the olefins of the at least two comonomers withthe catalyst used.

Metal catalyst as used in the present description may mean: a catalystproviding the catalytic reaction, wherein said catalyst comprises atleast one metal center that forms the active site. In the context of thepresent invention a “metal catalyst” is the same as a “transition metalcatalyst” wherein the metal is a transition metal.

Metal catalyst or a metal catalyst precursor according to the inventionmay be for example a single-site catalyst or Ziegler-Natta catalyst.

Catalyst precursor as used in the present description may mean: acompound that upon activation forms the active catalyst.

Single-site catalyst as used in the present description may meanespecially for example: a metal catalyst or catalyst precursor thatcontains exclusively one type of active site. A single-site catalyst canthereby be a metallocene, half-metallocene or post-metallocene.

Metallocene as used in the present description may mean: a metalcatalyst or catalyst precursor typically consisting of two substitutedcyclopentadienyl (Cp) ligands bound to a metal active site.

Half-metallocene as used in the present description may for examplemean: a metal catalyst or catalyst precursor typically consisting of onesubstituted cyclopentadienyl (Cp) ligand bound to a metal active site.

Post-metallocene as used in the present description may mean especiallyfor example: a metal catalyst that contains no substitutedcyclopentadienyl (Cp) ligands, but may contains one or more anions boundto the metal active site, typically via a heteroatom.

Ziegler-Natta catalyst as used in the present description means: atransition metal-containing solid catalyst compound comprises atransition metal halide selected from titanium halide, chromium halide,hafnium halide, zirconium halide, and vanadium halide, supported on ametal or metalloid compound (e.g. a magnesium compound or a silicacompound). An overview of such catalyst types is for example given by T.Pullukat and R. Hoff in Catal. Rev.—Sci. Eng. 41, vol. 3 and 4, 389-438,1999. The preparation of such a procatalyst is for example disclosed inWO96/32427 A1.

Transition metal as used in the present description may mean: a metalfrom any of the Groups 3-10 of the IUPAC Periodic Table of elements orin other words a Group 3 metal, a Group 4 metal, a Group 5 metal, aGroup 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal or aGroup 10 metal.

Co-catalyst as used in the present description may mean a compound thatactivates the catalyst precursor to obtain the active catalyst.

In an embodiment, the co-catalyst can be selected for example from thegroup consisting of MAO, DMAO, MMAO, SMAO, possibly in combination withaluminum alkyls, for example triisobutyl aluminum, and the combinationof an aluminum alkyl, for example triisobutyl aluminum, and fluorinatedaryl borane or fluorinated aryl borate.

In an embodiment, the co-catalyst can be selected for example fromaluminum alkyls and aluminum alkyl halides, such as for example triethylaluminum (TEA) or diethyl aluminum chloride (DEAC).

In an embodiment, the scavenger can be selected for example from thegroup consisting of trialkyl aluminum, for example triisobutyl aluminum,MAO, DMAO, MMAO, SMAO.

Scavenger as used in the present description may mean a compound thatscavenges impurities, especially protic and heteroatom containingcompounds, such as for example water, alcohols or acids, from thereaction medium prior and during the polymerization process. Theco-catalyst thereby also function for example as scavenger.

Olefins Suitable for Use in Step A)

Examples of suitable monomers include linear or branched α-olefins. Saidolefins preferably have between 2 and 30 carbon atoms, more preferablybetween 2 and 20 carbon atoms. Preferably, one or more of the followingare used: ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-cyclopentene, cyclohexene, norbornene,ethylidene-norbornene, and vinylidene-norbornene and one or morecombinations thereof. In addition, a combination of ethylene and/orpropylene on the one and one or more other olefins on the other hand isalso possible. Substituted analogues of the monomers discussed above mayalso be used, e.g. substituted by one or more halogens. In additionaromatic monomers can be used according to the present invention. It isalso possible to use a combination of two or more olefins.

Main Group Hydrocarbyl Functionality

The present invention uses at least one olefin monomer comprising a maingroup hydrocarbyl functionality. The present invention may for examplealso use said monomer in combination with other main group metal chaintransfer agents, for example zinc and/or magnesium and/or calcium and/oraluminum and/or boron and/or gallium hydrocarbyl/hydride chain transferagents.

The olefin monomer comprising a main group metal hydrocarbylfunctionality used in the present invention has a structure according toFormula 1a:R¹⁰⁰ _((n-2))R¹⁰¹M^(n+)R¹⁰²   Formula 1a

-   -   wherein: M is a main group metal; n is the oxidation state of M;        R¹⁰⁰, R¹⁰¹ and R¹⁰² are each independently selected from the        group consisting of a hydride, a C1-C18 hydrocarbyl group, or a        hydrocarbyl group Q on the proviso that at least one of R¹⁰⁰,        R¹⁰¹ and R¹⁰² is hydrocarbyl group Q. Wherein hydrocarbyl group        Q is according to Formula 1b:

-   -   wherein Z is bonded to M and is a C1-C18 hydrocarbyl group; R¹⁰⁵        optionally forms a cyclic group with Z; wherein R¹⁰³ and R¹⁰⁴        and R¹⁰⁵ are each independently selected from hydrogen or        hydrocarbyl;

In an embodiment, hydrocarbyl group Q is an α-olefin wherein Z is bondedto the main group metal, Z is a C1-C18 hydrocarbyl spacer group, R¹⁰³R¹⁰⁴ and R¹⁰⁵ are each hydrogen, said hydrocarbyl group Q beingaccording to Formula 1c:

In an embodiment, hydrocarbyl group Q is an alkene wherein Z is bondedto the main group metal, Z is a C1-C18 hydrocarbyl spacer group, R¹⁰³and R¹⁰⁴ are independently hydrogen or hydrocarbyl and R105 is a C1-18hydrocarbyl, said R¹⁰⁵ group forming a cyclic structure with Z, saidhydrocarbyl group Q being according to Formula 1d:

In an embodiment, said hydrocarbyl group Q can be an α-olefin accordingto Formula 1c or an unsaturated cyclic hydrocarbyl group according toFormula 1d. Preferably, hydrocarbyl group Q is an α-olefin or anunsaturated cyclic hydrocarbyl group.

Z is a branched or unbranched hydrocarbyl spacer group consisting ofbetween 1 and 18 carbon atoms, preferably 2 and 8 carbon atoms, morepreferably 4 and 7 carbon atoms, even more preferably 5 or 6 carbonatoms. Z is optionally substituted with hydrogen, carbon, andheteroatoms.

In an embodiment, hydrocarbyl group Q is an α-olefin according toFormula 1c. Said α-olefin has up to and including 30 carbon atoms, suchas up to and including 20 carbon atoms, preferably up to and including10 carbon atoms, such as ethenyl, propenyl, butenyl, heptenyl, hexenyl,septenyl, octenyl, nonenyl or decenyl and can be unbranched or branched.

In a preferred embodiment, said α-olefin is an unbranched α-olefinaccording to Formula 1e. In other words, the aluminum hydrocarbylfunctionality comprises at least one hydrocarbyl chain bearing anα-olefin (i.e. hydrocarbyl group Q). Said hydrocarbyl group Q is anα-olefin-comprising a main group metal.

In a preferred embodiment, hydrocarbyl group Q is an α-olefin accordingto Formula 1e where n is 1-5. In other words, the hydrocarbyl group Q is3-buten-1-yl, 4-penten-1-yl, 5-hexen-1-yl, 6-hepten-1-yl or 7-octen-1yl.

In an embodiment, the hydrocarbyl group Q is an unsaturated cyclichydrocarbyl group according to Formula 1d. In said cyclic olefin thealkene is situated between substituents R¹⁰⁵ and Z and R¹⁰⁵ forms atleast one ring with Z. R¹⁰⁵ can be a C1-C18 hydrocarbyl, which forms oneor more bonds with Z to form a cyclic group.

The number of R groups around the main group metal is dependent on theoxidization state of the metal. For example, when the main group metalis zinc or magnesium or calcium, the oxidation state is +2, and theformula is R¹⁰⁰MR¹⁰¹.

For example, when the main group metal is aluminum or boron or gallium,the oxidation state is +3, and the formula is R¹⁰⁰R¹⁰¹MR¹⁰².

In a preferred embodiment, at least one olefin comprising a main groupmetal hydrocarbyl functionality can be for example ethyl(7-octen1-yl)zinc or bis(7-octen-1-yl) zinc.

In a preferred embodiment, an olefin comprising at least one main groupmetal hydrocarbyl functionality can for example be selected from one ormore from the group of: di(isobutyl)(7-octen-1-yl) aluminum,di(isobutyl)(5-hexen-1-yl) aluminum, di(isobutyl)(3-buten-1-yl)aluminum, aluminum, tris(7-octen-1-yl) aluminum, tris(5-hexen-1-yl)aluminum and/or tris(3-buten-1-yl) aluminum.

In an embodiment, the copolymerization of at least one olefin comprisingmain group metal hydrocarbyl chain transfer agent functionality andanother α-olefin monomer may also for example be carried out in thepresence of an additional chain transfer agent or chain shuttling agent.

As non-limiting examples of chain transfer and/or chain shuttling agentsmain group metal hydrocarbyl or hydride chain transfer agents such asfor example the following be used: one or more hydrocarbyl or hydridegroups attached to a main group metal selected from aluminum, magnesium,calcium, zinc, gallium or boron.

Catalyst System Suitable for Use in Step A)

A catalyst system for use in step a) comprises at least two of thefollowing components:

-   -   i) a metal catalyst or metal catalyst precursor comprising a        metal from Group 3-10 of the IUPAC Periodic Table of elements        that can undergo chain transfer polymerization with the main        group metal hydrocarbyl functionality of the second type of        olefin monomer or that via a chain shuttling agent can undergo        chain transfer polymerization with the main group metal        hydrocarbyl functionality of the second type of olefin monomer;        and optionally at least one or more of    -   ii) a co-catalyst    -   iii) a scavenger

Moreover, an additional main group metal hydrocarbyl chain transferagent or a main group metal hydrocarbyl chain shuttling agent can beadded as additional chain transfer agents and/or chain shuttling agentsto insure reversible chain transfer polymerization.

The chain transfer agent functionality can also be a chain shuttlingagent functionality.

In an embodiment, the catalyst system used in step A) further comprisesan additional main group metal hydrocarbyl chain transfer agent or maingroup metal hydrocarbyl chain shuttling agent, selected from the groupconsisting of hydrocarbyl aluminum, hydrocarbyl magnesium, hydrocarbylzinc, hydrocarbyl gallium, hydrocarbyl boron, hydrocarbyl calcium,aluminum hydride, magnesium hydride, zinc hydride, gallium hydride,boron hydride, calcium hydride and a combination thereof. An additionalmain group metal hydrocarbyl chain transfer agent can also be a chainshuttling agent.

The comonomer, which can also act as chain transfer agent, may bepresent in a molar ratio of between 10:1 to 10000:1, preferred 20:1 to2000:1, further preferred between 100:1 to 500:1, compared to thecatalyst.

The chain shuttling agent may be present in a molar ratio of between 1:1to 1000:1, preferred 5:1 to 300:1, further preferred between 10:1 to100:1, compared to the catalyst.

Chain shuttling agent as used in the present description means: acompound that is capable of reversibly interchanging hydrocarbyls withcatalysts or other chain transfer agents. It is a metal compoundcomprising at least one ligand with a weak chemical bond. A chainshuttling agent can thus be a chain transfer agent.

Suitable catalysts and/or catalyst precursors are discussed in thissection as well as suitable co-catalysts and scavengers, which areoptional.

A catalyst for step A) can be used without co-catalyst, a catalystprecursor for step A) requires a co-catalyst to obtain the actual activecatalyst.

In the present invention, the catalyst may thereby preferably beselected so that it might undergo chain transfer polymerization with themain group metal hydrocarbyl functionality of the second type of olefinmonomer.

The catalyst may lead to chain transfer with a chain transfer agent,such as for example hydrogen or silanes.

One or more scavenger that can be used for example to scavengeimpurities from the reaction medium prior and during the polymerizationprocess, can be selected for example from the group consisting of:trialkyl aluminum, especially for example triisobutyl aluminum, MAO,DMAO, MMAO, SMAO.

Metal Catalyst and/or Catalyst Precursor Suitable for Step A)

In the section below several examples for metal catalysts or metalcatalyst precursors, which may be used to prepare the metal catalystaccording to the present invention, are specified. Metal catalysts thatare suitable for use in step A) of the present invention may be obtainedby reacting the metal catalyst precursors with a co-catalyst eitherprior to use in step A) or by in situ reaction with a co-catalyst.

According to the present invention, the metal catalyst has a metalcenter selected from a Group 3 metal, a Group 4 metal, a Group 5 metal,a Group 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal or aGroup 10 metal, preferably Y, Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd.

Ziegler-Natta catalysts as reported in US2009/0048399, US2014/0350200,WO96/32427, WO01/23441, WO2007/134851, U.S. Pat. No. 4,978,648, EP1283222A1, U.S. Pat. No. 5,556,820; U.S. Pat. No. 4,414,132; U.S. Pat. Nos.5,106,806 and 5,077,357 may also be suitable to use as metal catalystprecursors in the present invention.

The metal catalysts or metal catalyst precursors may for example be aC_(s)-, C₁- or C₂-symmetric zirconium or hafnium metallocene, preferablyan indenyl substituted zirconium or hafnium dihalide, more preferably abridged bis-indenyl zirconium or hafnium dihalide, even more preferablyrac-dimethylsilyl bis-indenyl zirconium or hafnium dichloride(rac-Me₂Si(Ind)₂ZrCl₂ and rac-Me₂Si(Ind)₂HfCl₂, respectively), orrac-dimethylsilyl bis-(2-methyl-4-phenyl-indenyl) zirconium or hafniumdichloride (rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ andrac-Me₂Si(2-Me-4-Ph-Ind)₂HfCl₂, respectively).

According to the invention, said catalyst precursor can be for example aso-called half-metallocene, or constrained geometry catalyst, even morepreferably, C₅Me₅[(C₆H₁₁)₃P═N]TiCl₂, [Me₂Si(C₅Me₄)N(tBu)]TiCl₂,[C₅Me₄(CH₂CH₂NMe₂]TiCl₂. According to the invention, said catalyst canbe for example a so-called post-metallocene, preferably[Et₂NC(N(2,6-iPr₂—C₆H₃)]TiCl₃ or[N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl.

The metal catalyst or metal catalyst precursor can also be for example apreferably C_(s) or C₁ symmetric compound according to the formula (C₅R⁸₄)R⁹(C₁₃R⁸ ₈)ML¹ _(n), where C₅R⁸ ₄ is an unsubstituted or substitutedcyclopentadienyl, and C₁₃R¹¹ ₈ is an unsubstituted fluorenyl group or asubstituted fluorenyl group; and the bridging R⁹ group is selected fromthe group consisting of —Si(Me)₂-, —Si(Ph)₂-, —C(Me)₂- or —C(Ph)₂-, thusproducing C₁- and C_(s)-symmetric metallocenes.

Non-limiting examples of zirconocene dichloride metal catalystprecursors suitable for use in the present invention include:bis(cyclopentadienyl) zirconium dichloride, bis(methyl-cyclopentadienyl)zirconium dichloride, bis(n-propyl-cyclopentadienyl) zirconiumdichloride, bis(n-butyl-cyclopentadienyl) zirconium dichloride,bis(1,3-dimethyl-cyclopentadienyl) zirconium dichloride,bis(1,3-di-t-butyl-cyclopentadienyl) zirconium dichloride,bis(1,3-ditrimethylsilyl-cyclopentadienyl) zirconium dichloride,bis(1,2,4-trimethyl-cyclopentadienyl) zirconium dichloride,bis(1,2,3,4-tetramethylcyclopentadienyl) zirconium dichloride,bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(indenyl)zirconium dichloride, bis(2-phenyl-indenyl) zirconium dichloride,bis(fluorenyl) zirconium dichloride, bis(tetrahydrofluorenyl) zirconiumdichloride, dimethylsilyl-bis(cyclopentadienyl) zirconium dichloride,dimethylsilyl-bis(3-t-butyl-cyclopentadienyl) zirconium dichloride,dimethylsilyl-bis(3-trimethylsilyl-cyclopentadienyl) zirconiumdichloride, dimethylsilyl-bis(tetrahydrofluorenyl) zirconium dichloride,dimethylsilyl-(1-indenyl)(cyclopentadienyl) zirconium dichloride,dimethylsilyl-(1-indenyl)(fluorenyl) zirconium dichloride,dimethylsilyl-(1-indenyl)(octahydrofluorenyl) zirconium dichloride,rac-dimethylsilyl-bis(2-methyl-3-t-butyl-cyclopentadienyl) zirconiumdichloride, rac-dimethylsilyl-bis(1-indenyl) zirconium dichloride,rac-dimethylsilyl-bis(4,5,6,7-tetrahydro-1-indenyl) zirconiumdichloride, rac-dimethylsilyl-bis(2-methyl-1-indenyl) zirconiumdichloride, rac-dimethylsilyl-bis(4-phenyl-1-indenyl) zirconiumdichloride, rac-dimethylsilyl-bis(2-methyl-4-phenyl-1-indenyl) zirconiumdichloride, rac-ethylene-bis(1-indenyl) zirconium dichloride,rac-ethylene-bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,rac-1,1,2,2-tetramethylsilanylene-bis(1-indenyl) zirconium dichloride,rac-1,1,2,2-tetramethylsilanylene-bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,rac-ethylidene(1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zirconium dichloride,rac-[1-(9-fluorenyl)-2-(2-methylbenzo[b]indeno[4,5-d]thiophen-1-yl)ethane]zirconiumdichloride, dimethylsilyl bis(cyclopenta-phenanthren-3-ylidene)zirconium dichloride, dimethylsilylbis(cyclopenta-phenanthren-1-ylidene) zirconium dichloride,dimethylsilyl bis(2-methyl-cyclopenta-phenanthren-1-ylidene) zirconiumdichloride, dimethylsilyl bis(2-methyl-3-benz-inden-3-ylidene) zirconiumdichloride,dimethylsilyl-bis[(3a,4,5,6,6a)-2,5-dimethyl-3-(2-methylphenyl)-6H-cyclopentathien-6-ylidene]zirconium dichloride,dimethylsilyl-(2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4(1H)-ylidene)(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,bis(2-methyl-1-cyclopenta-phenanthren-1-yl)zirconium dichloride,[ortho-bis(4-phenyl-2-indenyl) benzene] zirconium dichloride,[ortho-bis(5-phenyl-2-indenyl) benzene] zirconium dichloride,[ortho-bis(2-indenyl)benzene] zirconium dichloride, [ortho-bis(1-methyl-2-indenyl)benzene] zirconium dichloride,[2,2′-(1,2-phenyldiyl)-1,l′dimethylsilyl-bis(indenyl)] zirconiumdichloride, [2,2′-(1,2-phenyldiyl)-1,1′-(1,2-ethanediyl)-bis(indenyl)]zirconium dichloride, dimethylsilyl-(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilyl-(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylmethylene-(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene-(cyclopentadienyl)(fluorenyl)zirconium dichloride,dimethylmethylene-(cyclopentadienyl)(octahydrofluorenyl) zirconiumdichloride, diphenylmethylene-(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,dimethylmethylene-(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconiumdichloride,diphenylmethylene-(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconiumdichloride, dimethylmethylene-(3-methyl-1-cyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylmethylene-(3-methyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride,dimethylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride,diphenylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride, dimethylmethylene-(3-t-butyl-1-cyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylmethylene-(3-t-butyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride,dimethylmethylene-(3-ademantyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride,diphenylmethylene-(3-ademantyl-1-cyclopentadienyl)(fluorenyl) zirconiumdichloride,dimethylmethylene-(3-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,diphenylmethylene-(3-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,dimethylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,diphenylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,dimethylmethylene-(3-t-butyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,diphenylmethylene-(3-t-butyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,dimethylmethylene-(3-methyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,diphenylmethylene-(3-methyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,dimethylmethylene-(3-cyclohexyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,diphenylmethylene-(3-cyclohexyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,dimethylmethylene-(3-t-butyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,diphenylmethylene-(3-t-butyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,dimethylmethylene-(3-ademantyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride,diphenylmethylene-(3-ademantyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl)zirconium dichloride.

In a preferred embodiment, the metal catalyst or metal catalystprecursor can be for example:[[2,2′-[[[2-(dimethylamino-κN)ethyl]imino-κN]bis(methylene)]bis[4,6-bis(1,1-dimethylethyl)phenolato-κO]] zirconium dibenzyl,(phenylmethyl)[[2,2′-[(propylimino-κN)bis(methylene)]bis[4,6-bis(1,1-dimethylethyl)phenolato-κO]]zirconium dibenzyl or(phenylmethyl)[[2,2′-[[[(2-pyridinyl-κN)methyl]imino-κN]bis(methylene)]bis[4,6-bis(1,1-dimethylethyl)phenolato-κO]]zirconium dibenzyl.

In a preferred embodiment, complexes as reported in WO 00/43426, WO2004/081064, US 2014/0039138 Al, US 2014/0039139 Al and US 2014/0039140Al are suitable to use as metal catalyst precursors for the processes ofthe present invention.

Compounds analogous to those listed above but where Zr has been replacedby Hf, so called hafnocenes, may also be used according to the ascatalyst precursors present invention.

The metal catalysts or metal catalyst precursors for use in the presentinvention may also be from post-metallocene catalysts or catalystprecursors.

In a preferred embodiment, the metal catalyst or metal catalystprecursor may be: [HN(CH2CH2N-2,4,6-Me3-C6H2)2]Hf(CH2Ph)2 orbis[N,N′-(2,4,6-trimethylphenyl)amido)ethylenediamine]hafnium dibenzyl.

In a another preferred embodiment, the metal catalyst or metal catalystprecursor may be2,6-diisopropylphenyl-N-(2-methyl-3-(octylimino)butan-2) hafniumtrimethyl, 2,4,6-trimethylphenyl-N-(2-methyl-3-(octylimino)butan-2)hafnium trimethyl.

In a preferred embodiment, the metal catalyst or metal catalystprecursor may be[2,6-iPr2C6H3NC(2-iPr-C6H4)-2-(6-C5H6)]HfMe2-[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(□-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl.

Other non-limiting examples of metal catalyst precursors according tothe present invention are:[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl,[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α,α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium di(N,N-dimethylamido),[N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(α,α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride,[N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α,α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)] hafnium dimethyl,[N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin2-diyl)methane)] hafnium di(N,N-dimethylamido),[N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride. Other non-limiting examples include the family ofpyridyl diamide metal dichloride complexes such as:[N-[2,6-bis(1-methylethyl)phenyl]-6-[2-[phenyl(phenylamino-κN)methyl]phenyl]-2-pyridinemethanaminato(2-)-κN1,κN2]hafniumdichloride,[N-[2,6-bis(1-methylethyl)phenyl]-6-[2-[(phenylamino-κN)methyl]-1-naphthalenyl]-2-pyridinemethanaminato(2-)-κN1,κN2]hafnium dichloride,[N-[2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-[2-[(phenylamino-κN)methyl]phenyl]-2-pyridinemethanaminato(2-)-κN1,κN2]hafnium dichloride,[N-(2,6-diethylphenyl)-6-[2-[phenyl(phenylamino-κN)methyl]-1-naphthalenyl]-2-pyridinemethanaminato(2-)-κN1,κN2]zirconiumdichloride,[4-methyl-2-[[2-phenyl-1-(2-pyridinyl-κN)ethyl]amino-κN]phenolato(2-)-κO]bis(phenylmethyl)hafniumbis(phenylmethyl),[2-(1,1-dimethylethyl)-4-methyl-6-[[2-phenyl-1-(2-pyridinyl-κN)ethyl]amino-κN]phenolato(2-)-κO]hafnium bis(phenylmethyl),[2-(1,1-dimethylethyl)-4-methyl-6-[[phenyl(2-pyridinyl-κN)methyl]amino-κN]phenolato(2-)-κO]hafniumbis(phenylmethyl).

Non-limiting examples of titanium dichloride metal catalyst precursorssuitable for use in the present invention include:cyclopentadienyl(P,P,P-tri-t-butylphosphine imidato) titaniumdichloride, pentafluorophenylcyclopentadienyl(P,P,P-tri-t-butylphosphineimidato) titanium dichloride,pentamethylcyclopentadienyl(P,P,P-tri-t-butylphosphine imidato) titaniumdichloride,1,2,3,4-tetraphenyl-cyclopentadienyl(P,P,P-tri-t-butylphosphine imidato)titanium dichloride, cyclopentadienyl(P,P,P-tricyclohexylphosphineimidato) titanium dichloride, pentafluorophenylcyclopentadienyl(P,P,P-tricyclohexylphosphine imidato) titaniumdichloride, pentamethylcyclopentadienyl(P,P,P-tricyclohexylphosphineimidato) titanium dichloride,1,2,3,4-tetraphenyl-cyclopentadienyl(P,P,P-tricyclohexylphosphineimidato) titanium dichloride,pentamethylcyclopentadienyl(P,P-dicyclohexyl-P-(phenylmethyl)phosphineimidato) titanium dichloride,cyclopentadienyl(2,6-di-t-butyl-4-methylphenoxy) titanium dichloride,pentafluorophenylcyclopentadienyl(2,6-di-t-butyl-4-methylphenoxy)titanium dichloride,pentamethylcyclopentadienyl(2,6-di-t-butyl-4-methylphenoxy) titaniumdichloride,1,2,3-trimethyl-cyclopentadienyl(2,6-bis(1-methylethyl)phenolato)titanium dichloride,[(3a,4,5,6,6a-η)-2,3,4,5,6-pentamethyl-3aH-cyclopenta[b]thien-3a-yl](2,6-bis(1-methylethyl)phenolato)titanium dichloride,pentamethylcyclopentadienyl(N,N′-bis(1-methylethyl)ethanimidamidato)titanium dichloride,pentamethylcyclopentadienyl(N,N′-dicyclohexylbenzenecarboximidamidato)titanium dichloride,pentamethylcyclopentadienyl(N,N′-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,cyclopentadienyl(1,3-bis(1,1-dimethylethyl)-2-imidazolidiniminato)titanium dichloride,cyclopentadienyl(1,3-dicyclohexyl-2-imidazolidiniminato) titaniumdichloride,cyclopentadienyl(1,3-bis[2,6-bis(1-methylethyl)phenyl]-2-imidazolidiniminato)titanium dichloride,pentafluorophenylcyclopentadienyl(1,3-bis(1,1-dimethylethyl)-2-imidazolidiniminato)titanium dichloride,pentafluorophenylcyclopentadienyl(1,3-dicyclohexyl-2-imidazolidiniminato)titanium dichloride,pentafluorophenylcyclopentadienyl(1,3-bis[2,6-bis(1-methylethyl)phenyl]-2-imidazolidiniminato)titanium dichloride, pentamethylcyclopentadienyl(di-t-butylketimino)titanium dichloride,pentamethylcyclopentadienyl(2,2,4,4-tetramethyl-3-pentaniminato)titanium dichloride,[(3a,4,5,6,6a-η)-2,4,5,6-tetramethyl-3aH-cyclopenta[b]thien-3a-yl](2,2,4,4-tetramethyl-3-pentaniminato)titanium dichloride,cyclopentadienyl(N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,pentafluorophenylcyclopentadienyl(N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,pentamethylcyclopentadienyl(N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,cyclopentadienyl(2,6-difluoro-N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,pentafluorophenylcyclopentadienyl(2,6-difluoro-N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,pentamethylcyclopentadienyl(2,6-difluoro-N,N-bis(1-methylethyl)benzenecarboximidamidato)titanium dichloride,cyclopentadienyl(N,N-dicyclohexyl-2,6-difluorobenzenecarboximidamidato)titanium dichloride,pentafluorophenylcyclopentadienyl(N,N-dicyclohexyl-2,6-difluorobenzenecarboximidamidato)titanium dichloride,pentamethylcyclopentadienyl(N,N-dicyclohexyl-2,6-difluorobenzenecarboximidamidato)titanium dichloride, cyclopentadienyl(N,N,N′,N′-tetramethylguanidinato)titanium dichloride,pentafluorophenylcyclopentadienyl(N,N,N′,N′-tetramethylguanidinato)titanium dichloride,pentamethylcyclopentadienyl(N,N,N′,N′-tetramethylguanidinato) titaniumdichloride,pentamethylcyclopentadienyl(1-(imino)phenylmethyl)piperidinato) titaniumdichloride, pentamethylcyclopentadienyl chromium dichloridetetrahydrofuran complex.

Non-limiting examples of titanium (IV) dichloride metal catalystsuitable for use in the present invention are:(N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titaniumdichloride, (N phenylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titanium dichloride, (Nsec-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titaniumdichloride, (N sec-dodecylamido) (dimethyl)(fluorenyl)silane titaniumdichloride, (3 phenylcyclopentadien-1-yl) dimethyl(t-butylamido) silanetitanium dichloride, (3 (pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silane titanium dichloride,(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido) silane titaniumdichloride, 3 (3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido) silane titanium dichloride,(P-t-butylphospho)(dimethyl) (tetramethylcyclopentadienyl) silanetitanium dichloride. Other examples are the metal catalyst precursorcited in the list directly above wherein Ln is dimethyl, dibenzyl,diphenyl, 1,4-diphenyl-2-butene-1,4-diyl, 1,4-dimethyl-2-butene-1,4-diylor 2,3-dimethyl-2-butene-1,4-diyl.

Suitable metal catalyst precursors can be also the trivalent transitionmetal as those described in WO 9319104 (for example see especiallyexample 1, page 13, line 15).

Suitable metal catalyst precursors can be also the trivalent transitionmetal as [C5Me4CH2CH2N(n-Bu)2]TiCl2 described in WO 9613529 (for examplesee especially example III, page 20, line 10-13) or[C5H(iPr)3CH2CH2NMe2]TiCl2 described in WO 97142232 and WO 9742236 (forexample see especially example 1, page 26, line 14).

In an embodiment, the metal catalyst precursor is [C5H4CH2CH2NMe2]TiCl2;

In an embodiment, the metal catalyst or metal catalyst precursor mayalso be [C5Me4CH2CH2NMe2]TiCl2, [C5H4CH2CH2NiPr2]TiCl2,[C5Me4CH2CH2NiPr2]TiCl2, [C5H4C9H6N]TiCl2, [C5H4CH2CH2NMe2]CrCl2,[C5Me4CH2CH2NMe2]CrCl2; [C5H4CH2CH2NiPr2]CrCl2, [C5Me4CH2CH2NiPr2]CrCl2or [C5H4C9H6N]CrCl2.

A non-limiting list of examples of metal catalyst precursors that wouldbe suitable according to the present invention are: (N,Ndimethylamino)methyl-tetramethylcyclopentadienyl titanium dichloride,(N,N dimethylamino)ethyl-tetramethylcyclopentadienyl titaniumdichloride, (N,N dimethylamino)propyl-tetramethylcyclopentadienyltitanium dichloride, (N,N dibutylamino)ethyl-tetramethylcyclopentadienyltitanium dichloride, (pyrrolidinyl)ethyl-tetramethylcyclopentadienyltitanium dichloride, (N,N-dimethylamino)ethyl-fluorenyl titaniumdichloride,(bis(1-methyl-ethyl)phosphino)ethyl-tetramethylcyclopentadienyl titaniumdichloride,(bis(2-methyl-propyl)phosphino)ethyl-tetramethylcyclopentadienyltitanium dichloride,(diphenylphosphino)ethyl-tetramethylcyclopentadienyl titaniumdichloride,(diphenylphosphino)methyldimethylsilyl-tetramethylcyclopentadienyltitanium dichloride. Other examples are the catalysts cited in the listdirectly above wherein Ln wherein the chloride can be replaced withbromide, hydride, methyl, benzyl, phenyl, allyl,(2-N,N-dimethylaminomethyl)phenyl, (2-N,N-dimethylamino)benzyl,2,6-dimethoxyphenyl, pentafluorophenyl, and/or wherein the metal istrivalent titanium or trivalent chromium.

In a preferred embodiment, the catalyst precursor is:[2-(2,4,6-iPr3-C6H2)-6-(2,4,6-iPr3-C6H2)-C5H3N]Ti(CH2Ph)3 or[Et2NC(N-2,6-iPr2-C6H3)2]TiCl3

Other non-limiting examples of metal catalyst precursors according tothe present invention are:{N′,N″-bis[2,6-di(1-methylethyl)phenyl]-N,N-diethylguanidinato} titaniumtrichloride,{N′,N″bis[2,6-di(1-methylethyl)phenyl]-N-methyl-N-cyclohexylguanidinato}titanium trichloride,{N′,N″-bis[2,6-di(1-methylethyl)phenyl]-N,N-pentamethyleneguanidinato}titanium trichloride,{N′,N″-bis[2,6-di(methyl)phenyl]-sec-butyl-aminidinato} titaniumtrichloride,{N-trimethylsilyl,N′—(N″,N″-dimethylaminomethyl)benzamidinato} titaniumdichloride THF complex,{N-trimethylsilyl,N′—(N″,N″-dimethylaminomethyl)benzamidinato} vanadiumdichloride THF complex, {N,N′-bis(trimethylsilyl)benzamidinato} titaniumdichloride THF complex, {N,N′-bis(trimethylsilyl)benzamidinato} vanadiumdichloride THF complex.

In a preferred embodiment, the catalyst precursor can be for example:[C5H3N{CMe=N(2,6-iPr2C6H3)}2]FeCl2,[2,4-(t-Bu)2,-6-(CH═NC6F5)C6H2O]2TiCl2 orbis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)methyl] phenolato]titanium dichloride. Other non-limiting examples of metal catalystprecursors according to the present invention can be for example:bis[2-[(2-pyridinylimino)methyl]phenolato] titanium dichloride,bis[2-(1,1-dimethylethyl)-6-[(phenylimino)methyl]phenolato] titaniumdichloride,bis[2-(1,1-dimethylethyl)-6-[(1-naphthalenylimino)methyl]phenolato]titanium dichloride,bis[3-[(phenylimino)methyl][1,1′-biphenyl]-2-phenolato] titaniumdichloride,bis[2-(1,1-dimethylethyl)-4-methoxy-6-[(phenylimino)methyl]phenolato]titanium dichloride,bis[2,4-bis(1-methyl-1-phenylethyl)-6-[(phenylimino)methyl]phenolato]titanium dichloride,bis[2,4-bis(1,1-dimethylpropyl)-6-[(phenylimino)methyl]phenolato]titanium dichloride,bis[3-(1,1-dimethylethyl)-5-[(phenylimino)methyl][1,1′-biphenyl]-4-phenolato]titanium dichloride,bis[2-[(cyclohexylimino)methyl]-6-(1,1-dimethylethyl)phenolato] titaniumdichloride,bis[2-(1,1-dimethylethyl)-6-[[[2-(1-methylethyl)phenyl]imino]methyl]phenolato]titanium dichloride,bis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)ethyl]phenolato]titanium dichloride,bis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)propyl]phenolato]titanium dichloride,bis[2,4-bis(1,1-dimethylethyl)-6-[1-(phenylimino)ethyl]phenolato]titanium dichloride,bis[2,4-bis(1,1-dimethylethyl)-6-[1-(phenylimino)propyl]phenolato]titanium dichloride,bis[2,4-bis(1,1-dimethylethyl)-6-[phenyl(phenylimino)methyl]phenolato]titanium dichloride. Other examples are the metal catalyst precursorcited in the list directly above wherein the dichloride can be replacedwith dimethyl, dibenzyl, diphenyl, 1,4-diphenyl-2-butene-1,4-diyl,1,4-dimethyl-2-butene-1,4-diyl or 2,3-dimethyl-2-butene-1,4-diyl; and/orwherein the metal may be zirconium or hafnium.

In a preferred embodiment, the catalyst precursor can be:[2-[[[2-[[[3,5-bis(1,1-dimethylethyl)-2-(hydroxy-κO)phenyl]methyl]amino-κN]ethyl]methylamino-κN]methyl]-4,6-bis(1,1-dimethylethyl)phenolato(2-)-κO]titanium bis(phenylmethyl),[2,4-dichloro-6-[[[2-[[[3,5-dichloro-2-(hydroxy-κO)phenyl]methyl]amino-κN]ethyl]methylamino-κN]methyl]phenolato(2-)-κO]titanium bis(phenylmethyl),[2-[[[[1-[[2-(hydroxy-κO)-3,5-diiodophenyl]methyl]-2-pyrrolidinyl-κN]methyl]amino-κN]methyl]-4-methyl-6-tricyclo[3.3.1.13,7]dec-1-ylphenolato(2-)-κO]titanium bis(phenylmethyl),[2-[[[2-[[[[2-(hydroxy-κO)-3,5-bis(1-methyl-1-phenylethyl)phenyl]methyl]methylamino-κN]methyl]phenyl]methylamino-κN]methyl]-4,6-bis(1-methyl-1-phenylethyl)phenolato(2-)-κO]titanium bis(phenylmethyl),[2,4-dichloro-6-[[[2-[[[[3,5-dichloro-2-(hydroxy-κO)phenyl]methyl]amino-κN]methyl]phenyl]amino-κN]methyl]phenolato(2-)-κO]titanium bis(phenylmethyl). Other examples are the metal catalystprecursor cited in the list directly above wherein bis(phenylmethyl) canbe replaced with dichloride, dimethyl, diphenyl,1,4-diphenyl-2-butene-1,4-diyl, 1,4-dimethyl-2-butene-1,4-diyl or2,3-dimethyl-2-butene-1,4-diyl; and/or wherein the metal may bezirconium or hafnium.

A non-limiting list of examples of chromium catalysts that would besuitable for use in to the present invention are:(N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane chromiumbis(trimethylsilyl)methyl,(N-phenylamido)(dimethyl)(tetramethylcyclopentadienyl) silane chromiumbis(trimethyl)methyl, (N-sec-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane chromium bis(trimethylsilyl)methyl,(N-sec-dodecylamido)(dimethyl)(fluorenyl)silane chromium hydridetriphenylphosphine,(P-t-butylphospho)(dimethyl)(tetramethylcyclopentadienyl) silanechromium bis(trimethylsilyl)methyl. Other examples are the catalystscited in the list directly above wherein L1 is hydride, methyl, benzyl,phenyl, allyl, (2-N,N-dimethylaminomethyl)phenyl,(2-N,N-dimethylamino)benzyl; in other words chromium methyl, chromiumbenzyl, chromium allyl, chromium (2-N,N-dimethylamino)benzyl; and/orwherein the metal is trivalent yttrium or samarium; Other examples aremetal catalyst precursors as cited in the list directly above wherein Lnis chloride, bromide, hydride, methyl, benzyl, phenyl, allyl,(2-N,N-dimethylaminomethyl)phenyl, (2-N,N-dimethylamino)benzyl and/orwherein the metal is trivalent titanium or trivalent chromium.

Non-limiting examples of metal catalyst precursors according to thepresent invention are:N,N′-1,2-acenaphthylenediylidenebis(2,6-bis(1-methylethyl)benzenamine)nickel dibromide, N,N′-1,2-ethanediylidenebis(2,6-dimethylbenzenamine)nickel dibromide,N,N′-1,2-ethanediylidenebis(2,6-bis(1-methyl-ethyl)benzenamine) nickeldibromide, N,N′-1,2-acenaphthylenediylidenebis(2,6-dimethylbenzenamine)nickel dibromide,N,N′-1,2-acenaphthylenediylidenebis(2,6-bis(1-methylethyl)benzenamine)nickel dibromide,N,N′-1,2-acenaphthylenediylidenebis(1,1′-biphenyl)-2-amine nickeldibromide. Other examples are the catalysts cited in the list directlyabove wherein bromide can be replaced with chloride, hydride, methyl,benzyl and/or the metal can be palladium.

Further non-limiting examples of metal catalyst precursors according tothe present invention are:[2-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl]-6-(1,1-dimethylethyl)phenolato-κO]nickel phenyl(triphenylphosphine),[2-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl]-6-(1,1-dimethylethyl)phenolato-κO]nickel phenyl(triphenylphosphine),[2-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl]phenolato-κO] nickelphenyl(triphenylphosphine)-,[3-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl][1,1′-biphenyl]-2-olato-κO]nickel phenyl(triphenylphosphine)-,[2-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl]-4-methoxyphenolato-κO]nickel phenyl(triphenylphosphine),[2-[[[2,6-bis(1-methylethyl)phenyl]imino-κN]methyl]-4-nitrophenolato-κO]nickel phenyl(triphenylphosphine),[2,4-diiodo-6-[[[3,3″,5,5″-tetrakis(trifluoromethyl)[1,1′:3′,1″-terphenyl]-2′-yl]imino-κN]methyl]phenolato-κO]nickel methyl[[3,3′,3″-(phosphinidyne-κP)tris[benzenesulfonato]]]trisodium;[2,4-diiodo-6-[[[3,3″,5,5″-tetrakis(trifluoromethyl)[1,1′:3′,1″-terphenyl]-2′-yl]imino-κN]methyl]phenolato-κO]nickelmethyl[[3,3′-(phenylphosphinidene-κP)bis[benzenesulfonato]]]-disodium.

Co-Catalyst Suitable for Step A)

A co-catalyst can be used when a metal catalyst precursor is used. Aco-catalyst may thereby be an alkylating agent and/or reducing agentand/or cationization agent for the catalyst precursor and/or ascavenger. The function of this co-catalyst is to activate the metalcatalyst precursor. Co-catalyst may be selected for example fromaluminum alkyls and aluminum alkyl halides, such as for example triethylaluminum (TEA) or diethyl aluminum chloride (DEAC). Co-catalysts may beselected for example from the group consisting of MAO, DMAO, MMAO, SMAO,possibly in combination with aluminum alkyls, for example triisobutylaluminum, and/or with a combination of an aluminum alkyl, for exampletriisobutyl aluminum, and a fluorinated aryl borane or fluorinated arylborate (viz. B(R′)_(y) wherein R′ is a fluorinated aryl and y is 3 or 4,respectively). Examples of a fluorinated borane is B(C₆F₅)₃ and offluorinated borates are [X]⁺[B(C₆F₅)₄]⁻ (e.g. X=Ph₃C, C₆H₅N(H)Me₂).

Methylaluminoxane or MAO as used in the present description may mean: acompound derived from the partial hydrolysis of trimethyl aluminum thatserves as a co-catalyst for catalytic olefin polymerization.

Supported methylaluminoxane or SMAO as used in the present descriptionmay mean: a methylaluminoxane bound to a solid support.

Depleted methylaluminoxane or DMAO as used in the present descriptionmay mean: a methylaluminoxane from which the free trimethyl aluminum hasbeen removed.

Modified methylaluminoxane or MMAO as used in the present descriptionmay mean: modified methylaluminoxane, viz. the product obtained afterpartial hydrolysis of trimethyl aluminum plus another trialkyl aluminumsuch as tri(isobutyl) aluminum or tri-n-octyl aluminum.

Fluorinated aryl borates or fluorinated aryl boranes as used in thepresent description may mean: a borate compound having three or fourfluorinated (preferably perfluorinated) aryl ligands or a boranecompound having three fluorinated (preferably perfluorinated) arylligands.

For example, the co-catalyst can be an organometallic compound. Themetal of the organometallic compound can be selected from Group 1, 2, 12or 13 of the IUPAC Periodic Table of Elements. Preferably, theco-catalyst is an organoaluminum compound, more preferably analuminoxane, said aluminoxane being generated by the reaction of atrialkyl aluminum compound with water to partially hydrolyze saidaluminoxane. For example, trimethyl aluminum can react with water(partial hydrolysis) to form methylaluminoxane (MAO). MAO has thegeneral formula (Al(CH₃)_(3-n)O_(0.5n))_(x)·(AlMe₃)_(y) having analuminum oxide framework with methyl groups on the aluminum atoms.

MAO generally contains significant quantities of free trimethyl aluminum(TMA), which can be removed by drying the MAO to afford the so-calleddepleted MAO or DMAO. Supported MAO (SMAO) may also be used and may begenerated by the treatment of an inorganic support material, typicallysilica, by MAO.

Alternatively to drying the MAO, when it is desired to remove the freetrimethyl aluminum, a bulky phenol such as butylhydroxytoluene (BHT,2,6-di-t-butyl-4-methylphenol) can be added which reacts with the freetrimethyl aluminum.

Neutral Lewis acid modified polymeric or oligomeric aluminoxanes mayalso be used, such as alkylaluminoxanes modified by addition of a C1-30hydrocarbyl substituted Group 13 compound, especially a tri(hydrocarbyl)aluminum- or tri(hydrocarbyl) boron compounds, or a halogenated(including perhalogenated) derivatives thereof, having 1 to 10 carbonsin each hydrocarbyl or halogenated hydrocarbyl group, more especially atrialkyl aluminum compound.

Other examples of polymeric or oligomeric aluminoxanes are tri(isobutyl)aluminum- or tri(n-octyl) aluminum-modified methylaluminoxane, generallyreferred to as modified methylaluminoxane, or MMAO. In the presentinvention, MAO, DMAO, SMAO and MMAO may all be used as co-catalyst.

In addition, for certain embodiments, the metal catalyst precursors mayalso be rendered catalytically active by a combination of an alkylatingagent and a cation forming agent which together form the co-catalyst, oronly a cation forming agent in the case the catalyst precursor isalready alkylated, as exemplified in T. J. Marks et al., Chem. Rev.2000, (100), 1391. Suitable alkylating agents are trialkyl aluminumcompounds, preferably TIBA. Suitable cation forming agents for useherein include (i) neutral Lewis acids, such as C1-30 hydrocarbylsubstituted Group 13 compounds, preferably tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more preferably perfluorinated tri(aryl)boroncompounds, and most preferably tris(pentafluorophenyl) borane, (ii) nonpolymeric, compatible, non-coordinating, ion forming compounds of thetype [C]⁺[A]⁻ where “C” is a cationic group such as ammonium,phosphonium, oxonium, carbonium, silylium or sulfonium groups and [A]⁻is an anion, especially for example a borate.

Non-limiting examples of the anionic [“A”] are borate compounds such asC1-30 hydrocarbyl substituted borate compounds, preferablytetra(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more preferablyperfluorinated tetra(aryl)boron compounds, and most preferablytetrakis(pentafluorophenyl) borate.

A supported co-catalyst may also be used, for example using silicasupported MAO (SMAO) as the co-catalyst. The support material can be aninorganic material. Suitable supports include solid and particulatedhigh surface area, metal oxides, metalloid oxides, or mixtures thereof.Examples include: talc, silica, alumina, magnesia, titania, zirconia,tin oxide, aluminosilicates, borosilicates, clays, and mixtures thereof.

Preparation of a supported catalyst can be carried out using methodsknown in the art, for example i) a metal catalyst precursor can bereacted with supported MAO to produce a supported catalyst; ii) MAO canbe reacted with a metal catalyst precursor and the resultant mixture canbe added to silica to form the supported catalyst; iii) a metal catalystprecursor immobilized on a support can be reacted with soluble MAO.

Copolymerization of an Olefin and an Olefin Comprising a Main GroupMetal Hydrocarbyl Chain Transfer Agent Functionality

Step A) is preferably carried out in an inert atmosphere.

Copolymerization of the olefins can for example be carried out in thegas phase below the melting point of the polymer. Copolymerization canalso be carried out in the slurry phase below the melting point of thepolymer. Moreover, copolymerization can be carried out in solution attemperatures above the melting point of the polymer product.

It is known to continuously polymerize one or more olefins, such asethylene or propylene, in solution or in slurry, e.g. in a continuous(multi) CSTR or (multi) loop reactor, in the gas-phase in a reactor witha fluidized or mechanically stirred bed or in a combination of thesedifferent reactors, in the presence of a catalyst based on a compound ofa transition metal belonging to Groups 3 to 10 of the Periodic Table ofthe Elements.

Slurry phase polymerizations are typically carried out at temperaturesin the range 50-125° C. and at pressures in the range 1-50 bar.

The present invention may also be carried out in a solutionpolymerization process. Typically, in the solution process, the monomerand polymer are dissolved in an inert solvent.

Although a single reactor can be used, multiple reactors provide anarrower residence time distribution and therefore a better control ofmolecular weight distribution.

According to the present invention, content of comonomer can representfor example at between 0.01 mol-% and 70 mol-%, preferably between 0.05mol-% and 30 mol-%, preferably between 0.06 mol-% and 20 mol-%,preferably between 0.07 mol-% and 15 mol-%, preferably between 0.08mol-% and 10 mol-%, preferably between 0.09 mol-% and 8 mol-%,preferably between 0.1 mol-% and 7 mol-%, further preferred between 0.5mol-% and 5 mol-%, further preferred between 1 mol-% and 4 mol-%,further preferred between 2 mol-% and 3 mol-% and/or at least 0.001mol-%, further preferred least 0.01 mol-%, preferably 0.1 mol-%, furtherpreferred 0.5 mol-%, further preferred at least 1 mol-%, preferred atleast 10 mol-%, further preferred at least 15 mol-%, further preferredat least 20 mol-%, further preferred at least 30 mol-%, furtherpreferred at least 40 mol-%, further preferred at least 50 mol-%,further preferred at least 60 mol-% of the obtained polymers.

Step B) Oxidation

A second step of the process according to the present invention can bestep B) and relates to contacting the polyolefin obtained in step A)with at least one oxidizing agent or safe oxidizing agent to obtain toobtain a polyolefin having one or more pending oxidized and/or polarand/or nucleophilic functionalities. Step B) can, however, be optional,especially for example if a halogen or a halogen-containing compound isused as a quenching agent.

Typically the functionalization consists of an oxidation step followedby a subsequent quenching step to release the main group metal from theoxidized polyolefin chain (this can be for example by a hydrolysis stepin water). In this way, branched polyolefins bearing pending polarfunctionalities and/or branch functionalities, such as especially forexample alcohol functionalities or carboxylic acid functionalities, canbe obtained.

A quenching agent as used in the present description may mean: an agentto remove the main group metal from the polyolefin having one ormultiple main group metal-functionalized oxidized branches to obtainend-group functionalities and/or pending functionalities.

As safe oxidizing agent in step B) the following may for example beused: CO, CO₂, CS₂, COS, R²NCO, R²NCS, R²NCNR³, CH₂═C(R²)C(═O)OR³,CH₂═C(R²)(C═O)N(R³)R⁴, CH₂═C(R²)P(═O)(OR³)OR⁴, N₂O, R²CN, R²NC, epoxide,aziridine, cyclic anhydride, R³R⁴C═NR², carbodiimides, R²C(═O)R³,CIC(═O)OR² and SO₃, preferably N₂O, CO₂ and SO₃.

In an embodiment, an oxidizing agent or safe oxidizing agent used in thepresent invention can be dried. A dried safe oxidizing agent accordingto the invention can thereby preferably comprise less than 100 ppm ofwater, preferably less than 50 ppm of water, further preferred less than20 ppm of water, even more preferred less than 10 ppm of water, evenmore preferred less than 5 ppm of water, even more preferred less than 3ppm of water. This can contribute to improve oxidation yield.

With respect to CO, after quenching for example an aldehyde or ketonefunctionalized branched polyolefin (Pol-C(═O)H or Pol-C(═O)R¹) can beobtained.

With respect to R²NC, after quenching for example either (Pol-C(═NR²)Hor Pol-C(═NR²)R¹) can be obtained.

With respect to CO₂, after quenching for example either an acid or esterfunctionalized branched polyolefin (Pol-C(═O)OH or Pol-C(═O)OR¹) can beobtained.

With respect to CS₂, after quenching for example either Pol-C(═S)SH orPol-C(═S)SR¹ can be obtained.

With respect to COS, after quenching for example either Pol-C(═O)SH,Pol-C(═S)OH, Pol-C(═O)SR¹ or Pol-C(═S)OR¹) can be obtained.

With respect to R²NCO, after quenching for example amide or iminofunctionalized branched polyolefin (Pol-C(═O)NR²H, Pol-C(═NR²)OH,Pol-C(═O)NR²R¹ or Pol-C(═NR²)OR¹) can be obtained.

With respect to R²NCS, after quenching for example thiomidic acid,thioamide or thioamidate (ester) functionalized branched polyolefin(Pol-C(═S)NR²H, Pol-C(═NR²)SH, Pol-C(═S)NR²R¹ or Pol-C(═NR²)SR¹) can beobtained.

With respect to R²NCNR³, after quenching for example an amidefunctionalized branched polyolefin (Pol-C(═NR²)NR³R¹) can be obtained.

With respect to CH₂═CR²COOR³, after quenching for example either ahemiacetal or acetal functionalized branched polyolefin(Pol-CH₂CR²═C(OR³)OH or Pol-CH₂CR²═C(OR³)OR¹) can be obtained.

With respect to CH₂═C(R²)C(═O)NR³R⁴, after quenching for example afunctionalized branched polyolefin of formula Pol-CH₂—C(R²)═C(NR³R⁴)OR¹can be obtained.

With respect to CH₂═C(R²)P(═O)(OR³)OR⁴, after quenching for example afunctionalized branched polyolefin of formulaPol-CH₂—C(R²)═P(OR³)(OR⁴)OR¹ can be obtained.

With respect to N₂O, the metal carbon bond is cleaved and oxygen isinserted to form a Pol-O-M. After quenching for example either analcohol or an ether functionalized branched polyolefin (Pol-OH orPol-OR¹) can be obtained.

With respect to R²CN, after quenching for example either a substitutedor non-substituted imine functionalized branched polyolefin(Pol-C(R²)═NR¹ or Pol-C(R²)═NH) can be obtained.

With respect to epoxide, after quenching for example an alcohol, etheror ester functionalized branched polyolefin (Pol-C(R²)R³C(R⁴)R⁵OH,Pol-C(R²)R³C(R⁴)R⁵OR¹ or Pol-C(R²)R³C(R⁴)R⁵OC(═O)R¹) can be obtained.

With respect to aziridine, after quenching for example an amine or amidefunctionalized branched polyolefin (Pol-C(R²)R³C(R⁴)R⁵NR⁶H,Pol-C(R²)R³C(R⁴)R⁵NR⁶R¹ or Pol-C(R²)R³C(R⁴)R⁵NR⁶C(═O)R¹) can beobtained.

With respect to cyclic anhydride, after quenching for example either aanhydride-acid or anhydride-ester functionalized branched polyolefin(Pol-C(═O)—R²—C(═O)OH or Pol-C(═O)—R²—C(═O)OR) can be obtained.

With respect to imine, after quenching for example an aminefunctionalized branched polyolefin (Pol-CR³R⁴NR²H or Pol-CR³R⁴NR²R¹) canbe obtained.

With respect to SO₃, the metal carbon bond is cleaved and the oxidizingagent is inserted to form a Pol-S(═O)₂O-M. After quenching for exampleeither a sulfonic acid or sulfonic acid ester functionalized branchedpolyolefin (Pol-S(═O)₂OH or Pol-S(═O)₂OR¹) can be obtained.

With respect to a ketone or aldehyde, the metal carbon bond is cleavedand the oxidizing agent is inserted to form a Pol-C(R²)(R³)O-M. Afterquenching for example an alcohol, ether or ester functionalized branchedpolyolefin (Pol-CR²R³OH, Pol-CR²R³OR¹ or Pol-CR²R³OC(═O)R¹) can beobtained.

R¹, R², R³, R⁴, R⁵, R⁶ are each independently selected from the groupconsisting of H, SiR₃ ⁷, SnR₃ ⁷ or a C1-C16 hydrocarbyl, preferably aC1-C4 hydrocarbyl, where R⁷ is selected from the group consisting ofC1-C16 hydrocarbyl.

The oxidizing agent can be for example gaseous, whereby the oxidationstep can optionally be carried out for example at a pressure between0.01 and 80 bar, preferably between 1 and 20 bar, further preferredbetween 2 and 10 bar. In an embodiment, the oxidation step can becarried out for example at a temperature of between 0° C. and 250° C.

In an embodiment, the oxidation step can be for example carried out fora time period of between 0.5 minutes and 150 minutes, more preferablybetween 1 minutes and 120 minutes, further preferred between 30 minutesand 60 minutes depending on the reaction temperature and the oxidizingagent.

Step C) Quenching

During step C) a quenching agent can be used to remove the main groupmetal from the branches to obtain polar functionalities. Said quenchingstep can preferably be carried out using a hydrolyzing agent or anothernon-protic metal-substituting agent, which can for example remove themetal to obtain a polar functionality. Step C) can be optional,especially for example if a ketone, an ether or a thioether function isintroduced in Step B).

In an embodiment, said quenching agent is a hydrolyzing agent, which isa protic molecule, e.g. water or an alcohol, especially for example suchas (acidified) methanol or ethanol, preferably water.

This leads to a method for preparing polyolefins (Pols), such aspolyethylene (PE, HDPE, LLPDE), polypropylene (PP) and many othersbearing diverse end-group functionalities including, but not limited to,for example a halogen functionality (e.g. Pol-Cl), ketone functionality(Pol-C(═O)R), ketamine functionality (Pol-C(═NR²)R¹), carboxylic acidfunctionality (Pol-COOH), a thiolic acid functionality (Pol-C(═O)SH, athionic acid functionality (Pol-C(═S)OH), a dithio acid functionality(Pol-C(═S)SH), an alcohol functionality (Pol-OH), an ether functionality(Pol-OR¹), an amine functionality (Pol-N(R²)R¹), a thiol functionality(Pol-SH), an amidine functionality (Pol-C(═NR²)N(R³)R¹), an amidefunctionality (Pol-C(═O)N(R²)R¹), an ester functionality (Pol-C(═O)OR),a thioester functionality (Pol-C(═O)SR¹), a dithioester functionality(Pol-C(═S)SR¹) a hemiacetal (Pol-CH₂CR²═C(OR³)—OH) or an acetalfunctionality (Pol-CH₂CR²═C(OR³)—OR¹).

Pol as used in the present description means: polyolefin.

Content of polar functionalities, can represent for example at between0.01 mol-% and 60 mol-%, preferably between 0.05 mol-% and 25 mol-%,preferably between 0.07 mol-% and 15 mol-%, preferably between 0.08mol-% and 8 mol-%, preferably between 0.01 mol-% and 7 mol-%, preferablybetween 0.1 mol-% and 5 mol-%, further preferred between 0.5 mol-% and4.5 mol-%, further preferred between 1 mol-% and 4 mol-%, furtherpreferred between 2 mol-% and 3 mol-%, further preferred between 1.5mol-% and 2.5 mol-% and/or at least 0.001 mol-%, further preferred least0.01 mol-%, preferably 0.1 mol-%, further preferred 0.5 mol-%, furtherpreferred at least 1 mol-%, preferred at least 10 mol-%, furtherpreferred at least 15 mol-%, further preferred at least 20 mol-%,further preferred at least 30 mol-%, further preferred at least 40mol-%, further preferred at least 50 mol-%, further preferred at least60 mol-% of the obtained polymers.

A polymer with a relatively low content of polar functionalities and/orof comonomer can thereby for example ensure and be used to provide agood miscibility with polyolefins, while still contributing to improvecompatibility with more polar materials. On the other hand, a relativelyhigh content of polar functionalities and/or of comonomer can forexample contribute to improve compatibility with polar materials, othermaterials and/or barrier properties.

In an embodiment, branched polyolefins having one or multiple long chainbranches can have a number average molecular weight (M_(n)) between 500and 1,000,000 g/mol, preferably between 1,000 and 200,000 g/mol.

The polyolefins having one or multiple functionalized branches accordingto the present invention preferably have a polydispersity index (Ð orPDI) of between 1.1 and 10.0, more preferably between 1.1 and 5.0, morepreferably between 1.1 and 4.0, even more preferably between 1.5 and2.5.

Step D)

In step D) the polyolefin having one or more pending polarfunctionalities obtained in step C) is used to obtain a graft copolymerby transesterification of a preformed transesterifiable polymer,especially a preformed polyester and/or a preformed polycarbonate and/orby ring-opening polymerization of cyclic monomers, especially cyclicesters (lactones) and/or cyclic carbonates.

In step D) one or more side chains, especially polyester and/orpolycarbonate side chains, may thus be formed on the polyolefin mainchain, wherein as initiators the pending polar functionalities on thepolyolefin main chain obtained in step C) can be used to obtain a graftcopolymer. Thus, the product of step C) is subsequently used in step D)as a macro-initiator for the formation of graft copolymer.

Preformed transesterifiable polymer, especially preformed polyesterand/or a preformed polycarbonate, in the sense of the present inventionmay thereby mean for example commercially available or otherwiseprepared or obtained before and/or independently from at least one orpreferably all of the steps A), B), C) and D) according to theinvention.

Step D) can be carried out in a hydrocarbon solvent, especially forexample heptane, octane, decaline or an aromatic hydrocarbon solventlike toluene or xylene, or in other organic solvents, like DMF ortetrachloroethane, or in the melt.

A polyolefin-based graft copolymer obtained according to the presentinvention may comprise a first long chain branched polyolefin block andone or more polymer side chains and may have a number average molecularweight (M_(n)) between 500 and 1,000,000 g/mol, preferably between 2,000and 500,000 g/mol, preferably between 5,000 and 250,000 g/mol, furtherpreferred between 10,000 and 100,000 g/mol and/or a polydispersity index(Ð) of between 1.1 and 10.0, preferably between 2.0 and 5.0, wherebysaid polyolefin block may further optionally have for example abranching number determined by NMR of 0.2 to 10, preferably 0.5 to 5,even more preferred 1 to 3 per 10000 carbon atoms or of 50 to 3500,preferred 100 to 1000, further preferred 200 to 900 per 10000 carbonatoms.

A polyolefin-based graft copolymer according to the invention mayfurther also have polymer side chain(s), whereby the polymer side chaincomprise(s) at least one monomer that is different from the monomer(s)of the first long chain branched polyolefin block and/or wherein thegrafts are comprise ester and/or carbonate functionalities.

Moreover, the polymer side chain(s) may have a number average molecularweight (M_(n)) between 500 and 1,000,000 g/mol, preferably between 500and 100,000 g/mol, preferably between 500 and 50,000 g/mol, furtherpreferred between 500 and 25,000 g/mol, alternatively between 500 and10,000 g/mol, alternatively between 500 and 5,000 g/mol.

The polyolefin-based graft copolymers comprising a first long chainbranched polyolefin block and one or multiple polymer side chainsprepared according to the present invention may for example be used tointroduce polar properties to enhance the interfacial interactions inpolyolefins blends with polar polymers, such as for example blends withat least one polyester and/or at least one polycarbonate. They may beused for example as compatibilizers to improve properties such asadhesion. They may be used to improve barrier properties (especiallyagainst oxygen) and/or mechanical properties, like improved dimensionalstability and/or improved heat resistance and/or improved stiffness,especially for example for polyolefin films. They may be used ascompatibilizer to polar polymers such as for example starch or forpolyolefin-polar polymer blends, polyolefin-based composites withinorganic fillers, such as glass or talcum. They may be used in drugdelivery devices or for nanoporous materials/membranes. They maymoreover be used to improve adhesion to other materials, such as forexample glass and/or inorganic filers, to improve surface properties,such as for example paintability and/or printability, anti-fogging,anti-static properties. They may furthermore be used to improve chemicalresistance and/or acoustic properties for example by reduced squeakingand/or rattling and/or reduced weight.

Examples

The invention is further illustrated by the following non-limitingexamples merely used to further explain certain embodiments of thepresent invention.

General Considerations

All manipulations were performed under an inert dry nitrogen atmosphereusing either standard Schlenk or glove box techniques. Dry, oxygen freetoluene was employed as solvent for all polymerizations. Catalystsrac-Me₂Si(Ind)₂ZrCl₂, C₅Me₄(SiMe₂NtBu)TiCl₂ and rac-Me₂Si(Ind)₂HfCl₂were purchased from mCAT GmbH, Konstanz, Germany. Methylaluminoxane(MAO, 30 wt. % solution in toluene) was purchased from Chemtura.Tri(isobutyl)aluminum (TIBA, 1.0 M solution in hexanes),tetrachloroethane-d₂, diisobutylaluminum hydride solution (1.0 Msolution in THF) were purchased from Sigma Aldrich. Trityltetrakis(pentafluorophenyl)borate was purchased from Acros Organics.ω-Pentadecalactone (PDL) (98%, Sigma-Aldrich) was dried over CaH₂ anddistilled under reduced pressure. Toluene (Sigma-Aldrich) was driedusing an MBraun-SPS-800 purification column system.N′-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (98%,Sigma-Aldrich) was used as provided. Al(CH₃)₃ purchased from Aldrich wasused in 2 M solution in toluene.

Size Exclusion Chromatography (SEC).

The number average molecular weight (M_(n)) in g/mol and polydispersityindex (PDI) were determined by means of high temperature size exclusionchromatography (HT SEC) which was performed at 160° C. using a highspeed GPC (Freeslate, Sunnyvale, USA). Detection: IR4 (PolymerChar,Valencia, Spain). Column set: three Polymer Laboratories 13 μm PLgelOlexis, 300×7.5 mm. 1,2,4-Trichlorobenzene (TCB) was used as eluent at aflow rate of 1 mL·min⁻¹. TCB was freshly distilled prior to use. Themolecular weight was calculated from HT SEC analysis with respect tonarrow polyethylene standards (PSS, Mainz, Germany).

Synthesis of di(isobutyl)(oct-7-en-1-yl)aluminum (DIBAO)

Di(isobutyl)(oct-7-en-1-yl)aluminum (DIBAO) was synthesized byhydroalumination of excess 1,7-octadiene using di(isobutyl)aluminumhydride at 60° C. for 6 h in a 200 mL Schlenk flask equipped with amagnetic stirrer. The remaining reagents (for example 1,7-octadiene)after the hydroalumination reaction were removed by evacuation.

Copolymerization Procedure for the Preparation ofHydroxyl-Functionalized Long Chain Branched PE:

Copolymerization reactions ofethylene/di(isobutyl)(oct-7-en-1-yl)aluminum (DIBAO) were carried out instainless steel Büchi reactors (300 mL). Prior to the polymerization,the reactor was dried in vacuo at 40° C. and flushed with nitrogen.Solvent (toluene), MAO solution (30% w/w in toluene) were introducedinto the reactor and stirred at 150 rpm for 20-30 min. A solution ofdi(isobutyl)(oct-7-en-1-yl)aluminum (DIBAO) comonomer was introducedunder nitrogen atmosphere as a second type of olefin monomer comprisinga main group metal hydrocarbyl functionality followed by the addition ofthe predefined amount of diethyl zinc solution, used as chain shuttlingagent. The mixture was stirred for 10 min and saturated with lower flowof ethylene. The reaction was started by the addition of the predefinedamount 5 micromoles of the catalyst solution under an inert atmosphere.The reactor was then pressurized to the desired pressure (2 bars) withethylene and the pressure was maintained constant during thepolymerization time (30 min) at 40° C. At the end of the reaction, theethylene feed was stopped and the residual ethylene was vented off.Polymerization conditions for experiments 1 to 5 (Exp. 1 to 5) arelisted below in Table 1.

Oxidation

In-situ oxidation procedure using synthetic air: after releasing theresidual ethylene pressure, synthetic air was injected through a gasinjection tube and the suspension was maintained under constant oxygenpressure at 60° C. for 2 h with rigorous stirring (600 rpm) beforequenching with 300 mL of acidic methanol (10% concentrated HCl) toisolate the hydroxyl functionalized material. The resulting white powderwas then filtered, washed with methanol and dried at 60° C. in vacuoovernight.

TABLE 1 M_(n) cocat.: Act. T_(m) (kg/mol) Exp. Catalyst cocatalyst catcom:Zn:cat (kg/mol · h) (° C.)^(c) (PDI)^(d) 1 rac- MAO 760 250:25:12300 126.8  8.6 (2.9) Me₂Si(Ind)₂ZrCl₂ 2 rac- [Ph3C] 2.0 250:25:1 1620125.6 23.0 (3.0) Me₂Si(Ind)₂ZrCl₂ [B(C6F5)4 3 C₅Me₄(SiMe₂NtBu)TiCl₂ MAO800 300:20:1 1230 123.0 15.2 (3.5) 4 C₅Me₄(SiMe₂NtBu)TiCl₂ [Ph3C] 2.0300:20:1 1020 124.0 22.3 (3.0) [B(C6F5)4 5 rac- MAO 1000 300:20:1 960123.9 19.2 (2.3) Me₂Si(Ind)₂HfCl₂ 6 rac- [Ph3C] 2.0 300:20:1 780 125.529.3 (3.3) Me₂Si(Ind)₂HfCl₂ [B(C6F5)4

Synthesis of Al-Salen Catalyst

N,N′-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (2.0 g, 5.7 mmol)was suspended in toluene (30 mL) under N₂ flow. Subsequently, Al(CH₃)₃(2 M solution in toluene, 2.85 mL, 5.7 mmol) was added via syringe andthe mixture was stirred at room temperature. The thus obtained solutionwas concentrated to half the original volume and pale yellow needles ofAl-salen catalyst were isolated with a yield of 90%.

Typical Procedure for Synthesis of PE-Graft-PPDL Copolymers ViaCatalytic ROP.

A glass crimp cap vial was charged with PDL (1.15 g, 4.8 mmol) andAl-salen catalyst (1.68 mg, 5 μmol), hydroxyl-functionalized long chainbranched PE obtained in experiment 2 above (see Table 1, 5 μmol) andtoluene (1.50 g, 16.3 mmol). All manipulations were carried out in theglovebox. Then, the mixture was removed from the glovebox and stirred inan oil bath at 100° C. The progress of the reaction was followed by ¹HNMR spectroscopy by taking aliquots at set time intervals. Thesynthesized copolymer was cooled to room temperature and quenched usingacidified methanol, isolated and dried in vacuum at room temperature for18 h.

Typical Polymerization Procedure for the Preparation of PCL Via ROP ofCaprolactone.

In a glovebox, caprolactone (500 mg), Al-salen catalyst (74 μmol) and anequimolar amount of benzyl alcohol (8 mg, 74 μmol) were placed in asmall glass crimp cap vial. Dry toluene was added (1 mL) and the vialwas capped. The reaction mixture was removed from the glovebox and putin a carrousel reactor at 100° C. For all reactions, an aliquot of crudepolymer was withdrawn at the end of the polymerization reaction anddissolved in CDCl₃ in order to determine the conversion of the monomersby ¹H NMR spectroscopy. The reaction was then stopped by quenching thecrude product with acidic ethanol solution (5 mL) to precipitate thepolymer. The polymers were dried at 40° C. for 24 h under reducedpressure.

Typical Procedure for Synthesis of PE-Graft-PCL Copolymers ViaTransesterification.

The experiments were carried out in a micro compounder MC15 ml fromXplore equipped with co-rotating screws, a barrel with three 3temperature zones and a nitrogen purge at 150° C. (three temperaturezones set to 150° C.) with a screw RPM setting at 100.Hydroxyl-functionalized long chain branched PE obtained in experiment 2above (see Table 1, 8.0 g) and PCL (2.0 g, M_(n)=25.6 kg/mol, Ð=1.3,prepared with the Al-salen catalyst according to the method describedabove) were fed into a corotating twin screw micro compounder MC15 mlfrom Xplore equipped with co-rotating screws, a barrel with three 3temperature zones and a nitrogen purge at 150° C. (three temperaturezones set to 150° C.) with a screw RPM setting at 100. The polymers werepremixed for 5 minutes. Then the catalyst Sn(Oct)₂ (0.19 g, 0.5 mmol)was added and the mixture was stirred in the extruder for 2 minutes.After this time the extruder was evacuated. The copolymer was purifiedby dissolution in m-xylene at 120° C. and precipitation in a coldacetone. The copolymer was dried in a vacuum oven for 48 h at roomtemperature.

The invention claimed is:
 1. A process for the preparationpolyolefin-based graft copolymers comprising a first long chain branchedpolyolefin block and one or multiple polymer side chains, said processcomprising the step of: A) a polymerization step comprisingcopolymerizing at least one first type of olefin monomer and at leastone second type of olefin monomer comprising a main group metalhydrocarbyl functionality according to Formula 1a:R¹⁰⁰ _((n-2))R¹⁰¹M^(n+)R¹⁰²  Formula 1a using a catalyst system toobtain a polyolefin; wherein said catalyst system comprises a catalystor catalyst precursor comprising a metal from Group 3-10 of the IUPACPeriodic Table of elements that can undergo chain transferpolymerization with the main group metal hydrocarbyl functionality ofthe second type of olefin monomer or that via a chain shuttling agentcan undergo chain transfer polymerization with the main group metalhydrocarbyl functionality of the second type of olefin monomer, andoptionally at least one of a co-catalyst or a scavenger, and whereinfurther M is a main group metal; n is the oxidation state of M; R¹⁰⁰,R¹⁰¹ and R¹⁰² of Formula 1a are each independently selected from thegroup consisting of a hydride, a C1-C18 hydrocarbyl group, or ahydrocarbyl group Q on the proviso that at least one of R¹⁰⁰, R¹⁰¹ andR¹⁰² is a hydrocarbyl group Q, wherein hydrocarbyl group Q is accordingto Formula 1b:

wherein Z is bonded to M and Z is a C1-C18 hydrocarbyl group; R¹⁰⁵optionally forms a cyclic group with Z; wherein R¹⁰³ and R¹⁰⁴ and R¹⁰⁵are each independently selected from hydrogen or a hydrocarbyl group; B)an oxidizing step comprising contacting said polyolefin obtained in stepA) with at least one oxidizing agent to obtain a polyolefin having oneor more pending oxidized functionalities; a C) contacting saidpolyolefin obtained in step B) with at least one quenching agent toobtain a polyolefin having one or more pending polar functionalities,and D) using the polyolefin having one or more pending polarfunctionalities obtained in step C) to obtain a graft copolymer bytransesterification of a preformed transesterifiable polymer and/or byring-opening polymerization of cyclic monomers.
 2. A process accordingto claim 1, wherein said oxidizing agent used in step B) is an oxidizingagent according to Formula I:XY_(a)Z¹ _(b)Z² _(c)   Formula I wherein a is 1, b and c are eachindependently 0 or 1 and X, Y, Z¹ and Z² are independently selected fromcarbon, hydrocarbyl or heteroatom.
 3. A process according to claim 1,wherein the oxidizing agent used in step B) is selected from the groupconsisting of CO, CO₂, CS₂, COS, R²NCO, R²NCS, R²NCNR³,CH₂═C(R²)C(═O)OR³, CH₂═C(R₂)(C═O)N(R³)R⁴, CH₂═C(R²)P(═O)(OR³)OR⁴, N₂O,R²CN, R²NC, epoxide, aziridine, cyclic anhydride, R³R4C═NR², R²C(═O)R³,ClC(═O)OR² and SO₃.
 4. A process according to claim 1, wherein at leastone of R¹⁰⁰, R¹⁰¹ and R¹⁰² is a hydrocarbyl group Q and the remaininggroups of R¹⁰⁰, R¹⁰¹ and R¹⁰² are each a C1-C4 hydrocarbyl group orwherein two groups of R¹⁰⁰, R¹⁰¹ and R¹⁰² are each a hydrocarbyl group Qand the remaining group of R¹⁰⁰, R¹⁰¹ and R¹⁰² is a C1-C4 hydrocarbylgroup or wherein all of R¹⁰⁰, R¹⁰¹ and R¹⁰² are a hydrocarbyl group Q.5. A process according to claim 1, wherein the hydrocarbyl group Qaccording to Formula 1b attached to a main group metal is a linearα-olefin group or a cyclic unsaturated hydrocarbyl group.
 6. A processaccording to claim 1, wherein at least one type of olefin monomercomprises a main group metal hydrocarbyl functionality that is selectedfrom the group consisting of bis(isobutyl)(5-ethylen-yl-2-norbornene)aluminum, di(isobutyl)(7-octen-1-yl) aluminum,di(isobutyl)(5-hexen-1-yl) aluminum, di(isobutyl)(3-buten-1-yl)aluminum, tris(5-ethylen-yl-2-norbornene) aluminum, tris(7-octen-1-yl)aluminum, tris(5-hexen-1-yl) aluminum, or tris(3-buten-1-yl) aluminum,ethyl(5-ethylen-yl-2-norbornene) zinc, ethyl(7-octen-1-yl) zinc,ethyl(5-hexen-1-yl) zinc, ethyl(3-buten-1-yl) zinc,bis(5-ethylen-yl-2-norbornene) zinc, bis(7-octen-1-yl) zinc,bis(5-hexen-1-yl) zinc, or bis(3-buten-1-yl) zinc.
 7. A processaccording to claim 1, wherein the catalyst system comprises theco-catalyst, and the co-catalyst is selected from the group consistingof TEA, DEAC, MAO, DMAO, MMAO, SMAO, optionally in combination with analuminum alkyl.
 8. A process according to claim 1, wherein the metalcatalyst or metal catalyst precursor used in step A) comprises a metalfrom Group 3-8 of the IUPAC Periodic Table of elements.
 9. A processaccording to claim 8, wherein said metal catalyst or catalyst precursoris a Ziegler-Natta catalyst and/or a C_(s)-, C₁-, or C₂-symmetriczirconium metallocene.
 10. A process according to claim 8, wherein saidmetal catalyst or metal catalyst precursor is [Me₂Si(C₅Me₄)N(tBu)]TiCl₂,Me₂Si(2-Me-4-Ph-Ind)₂HfCl₂, [C₅Me₄CH₂CH₂N(n-Bu)₂]TiCl₂,bis(n-propyl-cyclopentadienyl)ZrCl₂, bis(n-butyl-cyclopentadienyl)ZrCl₂.11. A process according to claim 1, wherein the at least one type ofolefin monomer used in step A) is selected from the group consisting ofethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, cyclopentene, cyclohexene, norbornene,ethylidene-norbornene, and vinylidene-norbornene and one or morecombinations thereof.
 12. A process according to claim 1, wherein anadditional main group metal hydrocarbyl chain transfer agent is used instep A), and the additional main group metal hydrocarbyl chain transferagent is selected from the group consisting of: hydrocarbyl aluminum,hydrocarbyl magnesium, hydrocarbyl zinc, hydrocarbyl gallium,hydrocarbyl boron, hydrocarbyl calcium and one or more combinationsthereof.
 13. A polyolefin-based graft copolymer comprising a first longchain branched polyolefin block and one or multiple polymer side chainsobtained by a process according to claim 1, the polyolefin-based graftcopolymer having a number average molecular weight (M_(n)) between 500and 1,000,000 g/mol and having a polydispersity index (Ð) of between 1.1and 10.0 and wherein said polyolefin block has a branching numberdetermined by NMR of 0.2 to 10 per 10000 carbon atoms or of 50 to 3500per 10000 carbon atoms.
 14. A polyolefin-based graft copolymer accordingto claim 13, wherein the polymer side chain(s) comprise at least onemonomer that is different from the monomer(s) of the first long chainbranched polyolefin block and/or wherein the grafts are comprise esterand/or carbonate functionalities.
 15. A polyolefin-based graft copolymeraccording to claim 13, the polymer side chain(s) having a number averagemolecular weight (M_(n)) between 500 and 1,000,000 g/mol.
 16. A processaccording to claim 1, wherein the oxidizing agent used in step B) isselected from the group consisting of N₂O, CO₂ and SO₃.
 17. A processaccording to claim 1, wherein the hydrocarbyl group Q according toFormula 1b attached to a main group metal is but-3-en-1-yl,pent-4-en-1-yl, hex-5-en-1-yl, hept-6-en-1-yl or oct-7-en-1yl,5-ethylenebicyclo[2.2.1]hept-2-ene or5-propylenebicyclo[2.2.1]hept-2-ene.
 18. A process according to claim 1,wherein a metal catalyst or metal catalyst precursor used in step A)comprises a metal selected from the group consisting of Ti, Zr, Hf, V,Cr, Fe, Co, Ni, and Pd.
 19. A process according to claim 9, wherein saidmetal catalyst or catalyst precursor is a bridged bis-indenyl zirconiumdihalide.
 20. A process according to claim 7, wherein the oxidizingagent used in step B) is selected from the group consisting of N₂O, CO₂and SO₃; the hydrocarbyl group Q according to Formula 1b attached to amain group metal is but-3-en-1-yl, pent-4-en-1-yl, hex-5-en-1-yl,hept-6-en-1-yl or oct-7-en-1yl, 5-ethylenebicyclo[2.2.1]hept-2-ene or5-propylenebicyclo[2.2.1]hept-2-ene; a metal catalyst or metal catalystprecursor used in step A) comprises rac-dimethylsilyl bis-indenylzirconium dichloride (rac-Me₂Si(Ind)₂ZrCl₂) or rac-dimethylsilylbis-(2-methyl-4-phenyl-indenyl) zirconium dichloride(rac-Me₂Si(2-Me-4Ph-Ind)₂ZrCl₂; and the aluminum alkyl is triisobutylaluminum.
 21. A polyolefin-based graft copolymer according to claim 13,wherein the grafts comprise ester and/or carbonate functionalities. 22.A process according to claim 8, wherein the metal catalyst or catalystprecursor is a Ziegler-Natta catalyst.